JPWO2016158878A1 - タングステンカーバイドの製造方法 - Google Patents
タングステンカーバイドの製造方法 Download PDFInfo
- Publication number
- JPWO2016158878A1 JPWO2016158878A1 JP2017509988A JP2017509988A JPWO2016158878A1 JP WO2016158878 A1 JPWO2016158878 A1 JP WO2016158878A1 JP 2017509988 A JP2017509988 A JP 2017509988A JP 2017509988 A JP2017509988 A JP 2017509988A JP WO2016158878 A1 JPWO2016158878 A1 JP WO2016158878A1
- Authority
- JP
- Japan
- Prior art keywords
- tungsten
- tungsten carbide
- electrolytic solution
- raw material
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 85
- 239000010937 tungsten Substances 0.000 claims abstract description 85
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010304 firing Methods 0.000 claims description 33
- -1 alcohol amine Chemical class 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- JSELUEZGSGRXKT-UHFFFAOYSA-N 1-amino-2-methylpentan-2-ol Chemical compound CCCC(C)(O)CN JSELUEZGSGRXKT-UHFFFAOYSA-N 0.000 description 1
- XNIOWJUQPMKCIJ-UHFFFAOYSA-N 2-(benzylamino)ethanol Chemical compound OCCNCC1=CC=CC=C1 XNIOWJUQPMKCIJ-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 1
- GIACMWUKBLHAAG-UHFFFAOYSA-N 2-[hexyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCN(CCO)CCO GIACMWUKBLHAAG-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- KRGXWTOLFOPIKV-UHFFFAOYSA-N 3-(methylamino)propan-1-ol Chemical compound CNCCCO KRGXWTOLFOPIKV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- CETWDUZRCINIHU-UHFFFAOYSA-N methyl-n-amyl-carbinol Natural products CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5626—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on tungsten carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6264—Mixing media, e.g. organic solvents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/404—Refractory metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
電解槽は、特に限定されないが、例えば、図1に示す構成であってもよい。図1は、アノードとしてチタンバスケットを用いており、このチタンバスケットの中にタングステンを含む有価物を含有する原料混合物が設けられている。チタンバスケットは、本発明のような高電圧、高電流及び高温の電解処理条件で安定である点で好ましい。
また、特に炭素数が6を超えるアルコールアミンを含有する電解液を用いると、この後に行われるタングステン酸溶液の焼成工程を実施したとき、タングステンカーバイドを効率良くまた収率良く製造することができる。これは、タングステン酸溶液からタングステンカーバイドを焼成によって直接製造するとき、反応の進みすぎが良好に抑制されるため、生成したタングステンカーバイドがさらに還元されてタングステンを生成することが抑制されるためである。
電解槽のアノードとして、表1に示す品位の超硬材スクラップ10kgをチタンバスケットに入れたものを用いた。
電解槽のカソードとして、チタン板を用いた。
電解液に10mass%のモノエタノールアミンを用いて純水で20Lとした。電流密度を5A/dm2として、100Aの定電流で、温度を70℃にて電解溶解を10時間行った。
その結果、カソードのチタン板表面に金属コバルトが析出した。また、電解液にはタングステンが溶解しており、且つ、電解液中に残渣が生じた。また、タングステンの溶解量は0.6kgで電流効率はほぼ100%であった。
次に、タングステンが溶解した電解液を200℃で予備加熱して水分を減少させた後、水素雰囲気で、焼成温度までの昇温速度を50℃/分とし、1000℃で焼成した。XRDにより、タングステンカーバイドが90%生成し、タングステンが10%生成したことを確認した。
電解槽のアノードとして、表2に示す品位の超硬材スクラップ5kgをチタンバスケットに入れたものを用いた。
電解槽のカソードとして、チタン板を用いた。
電解液に10mass%のモノエタノールアミンを用いて純水で10Lとした。電流密度を10A/dm2として、100Aの定電流で、温度を70℃にて電解溶解を10時間行った。
その結果、カソードのチタン板表面に金属コバルトが析出した。また、電解液にはタングステンが溶解しており、且つ、電解液中に残渣が生じた。また、タングステンの溶解量は1.1kgで電流効率はほぼ100%であった。
次に、タングステンが溶解した電解液を200℃で予備加熱して水分を減少させた後、水素雰囲気で、焼成温度までの昇温速度を50℃/分とし、1100℃で焼成した。XRDにより、タングステンカーバイドが90%生成し、タングステンが10%生成したことを確認した。
水素雰囲気で、焼成温度までの昇温速度を30℃/分とし、830℃で焼成する以外は、実施例1と同様の処理を行った。XRDにより、タングステンカーバイドが78%、タングステンが22%生成したことを確認した。
水素雰囲気での焼成温度を700℃とした以外、実施例1と同様の原料を用いて同様に処理したところ、XRDにより、タングステンカーバイドが確認できず、タングステンがほぼ100%生成したことを確認した。
Claims (14)
- タングステンを含む有価物を含有する原料混合物に対して、有機系電解液を用いて電気分解を行うことで、前記電解液へタングステンを溶解させる工程と、
前記タングステンが溶解した電解液を800℃以上の温度で焼成することでタングステンカーバイドを得る工程と、
を含むことを特徴とするタングステンカーバイドの製造方法。 - 前記有機系電解液が有機系アルカリ電解液であることを特徴とする請求項1に記載のタングステンカーバイドの製造方法。
- 前記有機系アルカリ電解液がアルコールアミンを含有することを特徴とする請求項2に記載のタングステンカーバイドの製造方法。
- 前記アルコールアミンが、モノエタノールアミン及び/又はトリエタノールアミンであることを特徴とする請求項1〜3のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記電解液中のアルコールアミンの濃度が1〜50mass%であることを特徴とする請求項3又は4に記載のタングステンカーバイドの製造方法。
- 前記焼成工程における焼成温度までの昇温速度が5℃/分以上であることを特徴とする請求項1〜5のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記原料混合物が、タングステン以外の有価物を1〜60mass%含有することを特徴とする請求項1〜6のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記原料混合物が、タングステン以外の有価物を1〜30mass%含有することを特徴とする請求項7に記載のタングステンカーバイドの製造方法。
- 前記原料混合物が、タングステン以外の有価物を3〜10mass%含有することを特徴とする請求項8に記載のタングステンカーバイドの製造方法。
- 前記電解液の温度を20〜80℃に調整して電気分解を行うことを特徴とする請求項1〜9のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記電解液のpHが7以上であることを特徴とする請求項2〜10のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記タングステンが溶解した電解液を800℃以上の温度で焼成することでタングステンカーバイドを得る工程において、前記タングステンカーバイドと同時にタングステンも得ることを特徴とする請求項1〜11のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記電解液へタングステンを溶解させる工程の後、前記電解液に予備加熱を行うことで水分量を減少させた後、前記焼成を行い、タングステンカーバイドを得ることを特徴とする請求項1〜12のいずれか一項に記載のタングステンカーバイドの製造方法。
- 前記電気分解で使用するアノードが、前記タングステンを含む有価物を含有する原料混合物が設けられたチタンバスケットであることを特徴とする請求項1〜13のいずれか一項に記載のタングステンカーバイドの製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015071908 | 2015-03-31 | ||
JP2015071908 | 2015-03-31 | ||
PCT/JP2016/059970 WO2016158878A1 (ja) | 2015-03-31 | 2016-03-28 | タングステンカーバイドの製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2016158878A1 true JPWO2016158878A1 (ja) | 2018-02-01 |
JP6687603B2 JP6687603B2 (ja) | 2020-04-22 |
Family
ID=57006031
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016064478A Pending JP2016194152A (ja) | 2015-03-31 | 2016-03-28 | タングステン酸溶液の製造方法 |
JP2017509988A Active JP6687603B2 (ja) | 2015-03-31 | 2016-03-28 | タングステンカーバイドの製造方法 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016064478A Pending JP2016194152A (ja) | 2015-03-31 | 2016-03-28 | タングステン酸溶液の製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10227235B2 (ja) |
EP (1) | EP3279174B1 (ja) |
JP (2) | JP2016194152A (ja) |
KR (1) | KR102023265B1 (ja) |
CN (2) | CN107428618A (ja) |
TW (1) | TWI612013B (ja) |
WO (1) | WO2016158878A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6784510B2 (ja) * | 2016-05-17 | 2020-11-11 | Jx金属株式会社 | ポリタングステン酸アルコールアミンの製造方法 |
RU2752624C1 (ru) * | 2020-11-05 | 2021-07-29 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) | Электрохимический способ получения карбида молибдена |
TWI789246B (zh) * | 2022-02-18 | 2023-01-01 | 國立清華大學 | 含鎢合金的有價金屬元素回收方法 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5384812A (en) * | 1976-12-30 | 1978-07-26 | Toho Kinzoku Kk | Method of recovering metal component from metal carbide sintered member |
JPS54159325A (en) * | 1978-06-08 | 1979-12-17 | Mitsubishi Steel Mfg | Recovering waste catalyst |
US4374008A (en) * | 1981-06-01 | 1983-02-15 | Gte Laboratories Incorporated | Process for separating tungsten from coinage metals |
JPH09132413A (ja) * | 1995-05-23 | 1997-05-20 | Nanodyne Inc | 炭化タングステン及びタングステン系材料の再生方法 |
JPH10259057A (ja) * | 1996-12-05 | 1998-09-29 | Nanodyne Inc | 炭化金属の製法 |
JP2000203825A (ja) * | 1998-12-28 | 2000-07-25 | Plansee Tizit Ag | 純粋な炭化タングステン粉末を製造するための気体浸炭方法 |
US6524366B1 (en) * | 2000-09-22 | 2003-02-25 | N.V. Union Miniere S.A. | Method of forming nanograin tungsten carbide and recycling tungsten carbide |
JP2004034946A (ja) * | 2002-07-08 | 2004-02-05 | Toyota Motor Corp | 画像処理装置、駐車支援装置、及び画像処理方法 |
JP2004510668A (ja) * | 2000-09-29 | 2004-04-08 | オスラム・シルバニア・インコーポレイテッド | 炭化タングステン材料 |
JP2011032578A (ja) * | 2009-07-07 | 2011-02-17 | National Institute Of Advanced Industrial Science & Technology | 第5族元素及び/又は第6族元素の溶解方法 |
JP2013036111A (ja) * | 2011-08-10 | 2013-02-21 | Jx Nippon Mining & Metals Corp | タングステンの回収方法 |
JP2014129583A (ja) * | 2012-12-28 | 2014-07-10 | Jx Nippon Mining & Metals Corp | 高純度金属又は合金のスクラップからの金属又は合金の回収方法 |
JP2014173157A (ja) * | 2013-03-11 | 2014-09-22 | Jx Nippon Mining & Metals Corp | 粉状スクラップからの金属の回収方法 |
JP2015059068A (ja) * | 2013-09-19 | 2015-03-30 | 国立大学法人 新潟大学 | メソポーラス酸化タングステン及びその製造方法、光触媒、並びにメソポーラス酸化タングステン電極 |
US20150139872A1 (en) * | 2013-11-21 | 2015-05-21 | Kennametal Inc. | Purification of tungsten carbide compositions |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5329615A (en) | 1976-09-01 | 1978-03-20 | Nippon Gakki Seizo Kk | Manual ciear unit |
TW280839B (en) * | 1993-10-15 | 1996-07-11 | Nat Science Council | Process for recovery of tungsten carbide scraps by selective electrolysis |
US5384016A (en) | 1993-11-10 | 1995-01-24 | National Science Council | Process for recovering tungsten carbide from cemented tungsten carbide scraps by selective electrolysis |
US5942204A (en) | 1997-03-31 | 1999-08-24 | Omg Americas, Inc. | Method to produce a transition metal carbide from a partially reduced transition metal compound |
CN1724350A (zh) * | 2004-07-20 | 2006-01-25 | 中南大学 | 超细碳化钨粉末的制备方法 |
JP4916450B2 (ja) * | 2005-11-28 | 2012-04-11 | 株式会社アライドマテリアル | タングステン合金粒、それを用いた加工方法およびその製造方法 |
CN101575675B (zh) * | 2009-05-25 | 2011-08-10 | 刘嵘 | 利用硬质合金磨削废料生产铸造碳化钨的方法 |
JP5344170B2 (ja) | 2009-08-28 | 2013-11-20 | 三菱マテリアル株式会社 | タングステンの回収処理方法 |
CN102190299B (zh) * | 2010-03-18 | 2013-03-13 | 中国科学院上海硅酸盐研究所 | 一种纳米碳化钨粉体的制备方法 |
CN101780982B (zh) * | 2010-03-19 | 2011-07-27 | 郑州大学 | 一种碳化钨微纳米粉体的制备方法 |
CN101863472B (zh) * | 2010-06-25 | 2012-03-28 | 深圳市格林美高新技术股份有限公司 | 一种从废弃硬质合金回收碳化钨的方法 |
JP2013117064A (ja) * | 2011-11-04 | 2013-06-13 | Sumitomo Electric Ind Ltd | 溶融塩電解によるタングステンの製造方法及びその製造方法に使用する装置 |
JP5796716B2 (ja) | 2012-03-17 | 2015-10-21 | 三菱マテリアル株式会社 | コバルト含有液の不純物除去方法 |
US9447478B2 (en) * | 2012-04-27 | 2016-09-20 | Kyocera Corporation | Method for recovering tungsten compound |
CN103072987B (zh) * | 2012-12-20 | 2016-04-13 | 华南理工大学 | 一种制备金属碳化物或碳包覆金属碳化物的方法 |
CN103626233A (zh) * | 2013-12-02 | 2014-03-12 | 江西师范大学 | 一种三氧化钨纳米片及掺杂三氧化钨纳米片气体传感器 |
-
2016
- 2016-03-28 EP EP16772759.3A patent/EP3279174B1/en active Active
- 2016-03-28 WO PCT/JP2016/059970 patent/WO2016158878A1/ja active Application Filing
- 2016-03-28 CN CN201680020032.5A patent/CN107428618A/zh active Pending
- 2016-03-28 KR KR1020177030932A patent/KR102023265B1/ko active IP Right Grant
- 2016-03-28 CN CN202110358963.9A patent/CN113088703A/zh active Pending
- 2016-03-28 JP JP2016064478A patent/JP2016194152A/ja active Pending
- 2016-03-28 US US15/563,278 patent/US10227235B2/en active Active
- 2016-03-28 JP JP2017509988A patent/JP6687603B2/ja active Active
- 2016-03-30 TW TW105110016A patent/TWI612013B/zh active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5384812A (en) * | 1976-12-30 | 1978-07-26 | Toho Kinzoku Kk | Method of recovering metal component from metal carbide sintered member |
JPS54159325A (en) * | 1978-06-08 | 1979-12-17 | Mitsubishi Steel Mfg | Recovering waste catalyst |
US4374008A (en) * | 1981-06-01 | 1983-02-15 | Gte Laboratories Incorporated | Process for separating tungsten from coinage metals |
JPH09132413A (ja) * | 1995-05-23 | 1997-05-20 | Nanodyne Inc | 炭化タングステン及びタングステン系材料の再生方法 |
JPH10259057A (ja) * | 1996-12-05 | 1998-09-29 | Nanodyne Inc | 炭化金属の製法 |
JP2000203825A (ja) * | 1998-12-28 | 2000-07-25 | Plansee Tizit Ag | 純粋な炭化タングステン粉末を製造するための気体浸炭方法 |
US6524366B1 (en) * | 2000-09-22 | 2003-02-25 | N.V. Union Miniere S.A. | Method of forming nanograin tungsten carbide and recycling tungsten carbide |
JP2004510668A (ja) * | 2000-09-29 | 2004-04-08 | オスラム・シルバニア・インコーポレイテッド | 炭化タングステン材料 |
JP2004034946A (ja) * | 2002-07-08 | 2004-02-05 | Toyota Motor Corp | 画像処理装置、駐車支援装置、及び画像処理方法 |
JP2011032578A (ja) * | 2009-07-07 | 2011-02-17 | National Institute Of Advanced Industrial Science & Technology | 第5族元素及び/又は第6族元素の溶解方法 |
JP2013036111A (ja) * | 2011-08-10 | 2013-02-21 | Jx Nippon Mining & Metals Corp | タングステンの回収方法 |
JP2014129583A (ja) * | 2012-12-28 | 2014-07-10 | Jx Nippon Mining & Metals Corp | 高純度金属又は合金のスクラップからの金属又は合金の回収方法 |
JP2014173157A (ja) * | 2013-03-11 | 2014-09-22 | Jx Nippon Mining & Metals Corp | 粉状スクラップからの金属の回収方法 |
JP2015059068A (ja) * | 2013-09-19 | 2015-03-30 | 国立大学法人 新潟大学 | メソポーラス酸化タングステン及びその製造方法、光触媒、並びにメソポーラス酸化タングステン電極 |
US20150139872A1 (en) * | 2013-11-21 | 2015-05-21 | Kennametal Inc. | Purification of tungsten carbide compositions |
Non-Patent Citations (1)
Title |
---|
YABE HIDEKI ET AL.: "THE EFFECT OF SILVER ION ON ELECTRODEPOSITION OF TUNGSTEN AND TUNGSTEN CARBIDE FROM MOLTEN CHLORIDE", ELECTROCHIMICA ACTA, vol. 35, no. 1, JPN6016020102, pages 187 - 189, XP026516640, ISSN: 0004149650, DOI: 10.1016/0013-4686(90)85057-T * |
Also Published As
Publication number | Publication date |
---|---|
TWI612013B (zh) | 2018-01-21 |
CN107428618A (zh) | 2017-12-01 |
CN113088703A (zh) | 2021-07-09 |
EP3279174A1 (en) | 2018-02-07 |
KR20170132810A (ko) | 2017-12-04 |
US20180072576A1 (en) | 2018-03-15 |
TW201718401A (zh) | 2017-06-01 |
JP2016194152A (ja) | 2016-11-17 |
US10227235B2 (en) | 2019-03-12 |
WO2016158878A1 (ja) | 2016-10-06 |
EP3279174B1 (en) | 2019-12-18 |
KR102023265B1 (ko) | 2019-09-19 |
JP6687603B2 (ja) | 2020-04-22 |
EP3279174A4 (en) | 2018-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5329615B2 (ja) | タングステンの回収方法 | |
JP6594411B2 (ja) | タングステンの製造方法 | |
JP6687603B2 (ja) | タングステンカーバイドの製造方法 | |
KR102011588B1 (ko) | 텅스텐을 포함하는 유가물의 회수 방법 | |
JP2014070261A (ja) | 遷移金属の回収方法 | |
JP6784510B2 (ja) | ポリタングステン酸アルコールアミンの製造方法 | |
JP6258995B2 (ja) | 遷移金属の回収方法 | |
WO2016159195A1 (ja) | 金属ポリ酸及び金属ポリ酸の製造方法 | |
JP2023097401A (ja) | パラジウム抽出方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181214 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191112 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200114 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200303 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200402 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6687603 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |