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
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- 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
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- Prior art keywords
- tungsten
- tungsten carbide
- electrolytic solution
- raw material
- temperature
- Prior art date
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- 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
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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。
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