JP7396391B2 - 次亜塩素酸生成電極 - Google Patents
次亜塩素酸生成電極 Download PDFInfo
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- JP7396391B2 JP7396391B2 JP2022059482A JP2022059482A JP7396391B2 JP 7396391 B2 JP7396391 B2 JP 7396391B2 JP 2022059482 A JP2022059482 A JP 2022059482A JP 2022059482 A JP2022059482 A JP 2022059482A JP 7396391 B2 JP7396391 B2 JP 7396391B2
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- hypochlorous acid
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 title claims description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 14
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 13
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000020679 tap water Nutrition 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 235000020681 well water Nutrition 0.000 claims description 2
- 239000002349 well water Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 229910052703 rhodium Inorganic materials 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- -1 etc. Chemical compound 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Classifications
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/26—Chlorine; Compounds thereof
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- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
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Description
チタン又はチタン合金からなる電極基体と、
前記電極基体と電気的に接合された複合層とを有し、
前記複合層が、イリジウムまたはその化合物と、タンタルまたはその化合物と、ルテニウムまたはその化合物および/または白金とを含んでなり、かつ、酸化ロジウムを含まないことを特徴とするものである。
本発明による電極は、チタン又はチタン合金からなる電極基体と、この基体と電気的に接合された複合層とを少なくとも備える基本構造を有する。そして、基体に接合された複合層が、イリジウムまたはその化合物と、タンタルまたはその化合物と、ルテニウムまたはその化合物および/または白金とを含んでなり、かつ、酸化ロジウムを含まないことを特徴とする。
本発明において、電極基体として、チタンまたはチタン合金を用いる。チタン合金としては、チタンを主体とする耐食性のある導電性の合金を使用することができ、例えば、Ti-Ta-Nb、Ti-Pd、Ti-Zr、Ti-Al等の組み合わせからなる、通常電極材料として使用されているチタン基合金が挙げられる。これらの電極材料は板状、有孔板状、棒状、網板状等の所望形状に加工して電極基材として用いることができる。なお、本発明にあって、電極基体の表面に酸化チタン膜が形成されることは排除されない。
本発明による電極は、上記した電極基体と電気的に接合された複合層を備え、この複合層は、上記したように、イリジウムまたはその化合物と、タンタルまたはその化合物と、ルテニウムまたはその化合物および/または白金とを含んでなり、かつ、酸化ロジウムを含まないことを特徴とする。本発明による電極の複合層は、酸化ロジウムを含まないことを特徴とするが、本発明が提案する複合層の組成は、従来公知のロジウム含有電極のロジウムを、ルテニウムおよび/または白金と置き換えた組成と理解することもできる。したがって、本発明による電極の複合層の組成は、従来公知の、あるいはこれから提案されるロジウムを含む次亜塩素酸生成用電極の組成において、ロジウムをルテニウムおよび/または白金と置き換えたものとして決定されてよい。
本発明による電極は、次亜塩素酸の生成能および電極の耐久性に優れる。具体的には、本発明による電極は次亜塩素酸を0.2ppm以上の濃度で生成できる性能を備え、さらにこの性能は、好ましくは通電時間500時間を経過しても維持される。
本発明による電極は、上記したように、従来公知のロジウムを含む電極において、ロジウムを、ルテニウムおよび/または白金と置き換えた組成の複合層を備えるものと理解できるから、その製造も、ロジウムをルテニウムおよび/または白金と置き換えた以外は、従来の電極と同様の方法により、好ましく製造することができる。具体的には、特許文献1または2の記載に準じて、製造することができる。
基材の用意
JIS1種相当のチタン板素材(t0.5mm×w100mm×l100mm)をアルコール洗浄後、20℃の8重量%フッ化水素酸水溶液中で2分間、そして120℃の60重量%硫酸水溶液中で3分間処理した。次いで、チタン基体を硫酸水溶液から取り出し、冷水を噴霧し急冷した。さらに、20℃の0.3重量%フッ化水素酸水溶液中に2分間浸漬した後水洗した。水洗後、400℃の大気中で1時間加熱処理して、チタン基体表面に薄い酸化チタンの中間層を形成させた。
複合層の形成のための前駆体を含む溶液を次のように用意した。すなわち、ルテニウム濃度100g/Lに調整した塩化ルテニウムのブタノール溶液とイリジウム濃度200g/Lに調整した塩化イリジウム酸のブタノール溶液とタンタル濃度200g/Lに調整したタンタルエトキシドのブタノール溶液と白金濃度200g/Lに調整した塩化白金酸のブタノール溶液をPt-Ir-Ru-Taの組成比が下記表-1に示すモル%となるようにそれぞれ秤量し、次いでIrの金属換算濃度が50g/Lとなるようにブタノールにて希釈し、下記表に示す実施例1~8を調製した。また、上記塩化ルテニウムを、塩化ロジウムとし、白金およびルテニウム前駆体を含まない溶液を比較例として調製した。
実施例1~8および比較例の電極を、室温、水道水中にて9.7A/dm2で電解した後、極性を切替えて-9.7A/dm2で電解する操作を繰返す電解を行い、一定時間経過後の電解時の次亜塩素酸濃度をDPD法にて測定していき、電解によって生成した次亜塩素酸濃度が0.2ppm未満となった時の電解時間を記録した。その結果は、下記表1に示されるとおりであった。
Claims (8)
- 塩化物イオンを含む水を電解して、次亜塩素酸の生成に用いられる電極であって、
チタン又はチタン合金からなる電極基体と、
前記電極基体と電気的に接合された複合層とを有し、
前記複合層が、イリジウムまたはその化合物と、タンタルまたはその化合物と、ルテニウムまたはその化合物および/または白金とを含んでなり、かつ、酸化ロジウムを含まず、
前記複合層が、金属換算で、イリジウム32~43mol%と、タンタル25~36mol%と、ルテニウム8~22mol%と、そして白金10~23mol%とを含んでなることを特徴とする、電極。 - 前記複合層が、酸化イリジウムと、酸化タンタルと、酸化ルテニウムと、白金とからなる、請求項1に記載の電極。
- 前記ルテニウムが11~19mol%であり、前記白金が13~20mol%である、請求項1又は2に記載の電極。
- 前記ルテニウムと白金との合計が、金属換算で24mol%~39mol%である、請求項3に記載の電極。
- 前記塩化物イオンを含む水が水道水または井戸水である、請求項1~4のいずれか一項に記載の電極。
- 請求項1~5のいずれか一項に記載の電極を備える、次亜塩素酸水生成装置。
- 次亜塩素酸水を生成する装置を備え、当該装置が、請求項1~5のいずれか一項に記載の電極を備えるものであることを特徴とするトイレ装置。
- 請求項1~5のいずれか一項に記載の電極を用意し、
前記電極と、塩化物イオンを含む水とを接触させること
を含んでなる、次亜塩素酸水を製造する方法。
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JP2006515389A (ja) | 2003-03-24 | 2006-05-25 | エルテック・システムズ・コーポレーション | 白金族金属を有する電気触媒コーティング及びこれから製造された電極 |
JP2006322026A (ja) | 2005-05-18 | 2006-11-30 | Furuya Kinzoku:Kk | 電解的水処理電極及び装置 |
JP2008050675A (ja) | 2006-08-28 | 2008-03-06 | Ishifuku Metal Ind Co Ltd | 電解用電極 |
CN105967281A (zh) | 2016-06-16 | 2016-09-28 | 中国船舶重工集团公司第七二五研究所 | 一种钛基亚氧化钛电极制备方法 |
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