JP5680655B2 - 電解法のための陰極 - Google Patents
電解法のための陰極 Download PDFInfo
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- JP5680655B2 JP5680655B2 JP2012532586A JP2012532586A JP5680655B2 JP 5680655 B2 JP5680655 B2 JP 5680655B2 JP 2012532586 A JP2012532586 A JP 2012532586A JP 2012532586 A JP2012532586 A JP 2012532586A JP 5680655 B2 JP5680655 B2 JP 5680655B2
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- 238000005868 electrolysis reaction Methods 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 claims description 60
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 44
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 13
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005422 blasting Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000007353 oxidative pyrolysis Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic material
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- 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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
- C25B11/097—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 comprising two or more noble metals or noble metal alloys
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- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Electrochemistry (AREA)
- Ceramic Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、Pr(III) ニトレート(50g/l)およびPd(II) ニトレート(20g/l)の水溶液を5回の塗りで塗布し、1回の塗布ごとに450℃における15分間の熱処理を行い、それにより1.90g/m2 のPt、1.24g/m2 のPdおよび3.17g/m2 のPrからなる堆積を得た(内側の触媒層の形成)。このようにして得られた触媒層の上に、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、Pr(III) ニトレート(27g/l)およびPd(II) ニトレート(20g/l)を含む第二の溶液を4回の塗りで塗布し、1回の塗布ごとに450℃における15分間の熱処理を行い、それにより1.77g/m2 のPt、1.18g/m2 のPdおよび1.59g/m2 のPrからなる堆積を得た(外側の触媒層の形成)。
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、Pr(III) ニトレート(50g/l)およびPd(II) ニトレート(20g/l)の水溶液を3回の塗りで塗布し、1回の塗布ごとに460℃における15分間の熱処理を行い、それにより1.14g/m2 のPt、0.76g/m2 のPdおよび1.90g/m2 のPrからなる堆積を得た(内側の触媒層の形成)。このようにして得られた触媒層の上に、硝酸で酸性化されたPt(II)ジアミノジニトレート(23.4g/l)、Pr(III) ニトレート(27g/l)およびPd(II) ニトレート(20g/l)を含む第二の溶液を6回の塗りで塗布し、1回の塗布ごとに460℃における15分間の熱処理を行い、それにより1.74g/m2 のPt、1.49g/m2 のPdおよび2.01g/m2 のPrからなる堆積を得た(外側の触媒層の形成)。
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたRu(III)ニトロシルニトレート(30g/l)、Pr(III) ニトレート(50g/l)、Pd(II) ニトレート(16g/l)およびAgNo3(4g/l)の水溶液を5回の塗りで塗布し、1回の塗布ごとに430℃における15分間の熱処理を行い、それにより1.90g/m2 のRu、1.01g/m2 のPd、0.25g/m2 のAgおよび3.17g/m2 のPrからなる堆積を得た(内側の触媒層の形成)。このようにして得られた触媒層の上に、硝酸で酸性化されたRu(III)ニトロシルニトレート(30g/l)、Pr(III) ニトレート(27g/l)、Pd(II) ニトレート(16g/l)およびAgNo3(4g/l)を含む第二の溶液を6回の塗りで塗布し、1回の塗布ごとに430℃における15分間の熱処理を行い、それにより2.28g/m2 のRu、1.22g/m2 のPd、0.30g/m2 のAgおよび2.05g/m2 のPrからなる堆積を得た(外側の触媒層の形成)。
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、La(III) ニトレート(50g/l)およびPd(II) ニトレート(20g/l)の水溶液を5回の塗りで塗布し、1回の塗布ごとに450℃における15分間の熱処理を行い、それにより1.90g/m2 のPt、1.24g/m2 のPdおよび3.17g/m2 のLaからなる堆積を得た(内側の触媒層の形成)。このようにして得られた触媒層の上に、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、La(III) ニトレート(32g/l)およびPd(II) ニトレート(20g/l)を含む第二の溶液を3回の塗りで塗布し、1回の塗布ごとに450℃における15分間の熱処理を行い、それにより1.14g/m2 のPt、0.76g/m2 のPdおよび1.22g/m2 のLaからなる堆積を得た(外側の触媒層の形成)。
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、Pr(III) ニトレート(50g/l)、Rh(III)クロリド(4g/l)およびPd(II) ニトレート(20g/l)の水溶液を7回の塗りで塗布し、1回の塗布ごとに450℃における15分間の熱処理を行い、それにより2.66g/m2 のPt、1.77g/m2 のPd、0.44g/m2 のRhおよび4.43g/m2 のPrからなる堆積を得た(WO2008/043766号に従う触媒層の形成)。
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、Pr(III) ニトレート(50g/l)およびPd(II) ニトレート(20g/l)の水溶液を7回の塗りで塗布し、1回の塗布ごとに460℃における15分間の熱処理を行い、それにより2.80g/m2 のPt、1.84g/m2 のPdおよび4.70g/m2 のPrからなる堆積を得た(触媒層の形成)。
100mm×100mm×0.89mmの寸法のニッケル200のメッシュがコランダム(鋼玉石)を用いてブラスト処理(吹付け処理)に供され、次いで20%の沸騰したHCl中で5分間エッチングされた。次いで、このメッシュに、硝酸で酸性化されたPt(II)ジアミノジニトレート(30g/l)、Pr(III) ニトレート(28g/l)およびPd(II) ニトレート(20g/l)の水溶液を6回の塗りで塗布し、1回の塗布ごとに480℃における15分間の熱処理を行い、それにより2.36g/m2 のPt、1.57g/m2 のPdおよび2.20g/m2 のPrからなる堆積を得た(触媒層の形成)。
[1]
電解法のための陰極であって、金属基板と、この基板に設けられた少なくとも一つの内側の触媒層と一つの外側の触媒層とを含む多層の触媒被覆からなり、内側の触媒層と外側の触媒層の両者はパラジウム、少なくとも一つの希土類元素、および白金とルテニウムのいずれかから選択される少なくとも一つの貴金属成分を含み、このとき前記外側の触媒層は10〜45重量%の希土類元素の含有量を有し、そして前記内側の触媒層は前記外側の触媒層の前記含有量よりも高い希土類元素の含有量を有する、前記陰極。
[2]
前記外側の触媒層は30〜40重量%の希土類元素の含有量を有し、そして前記内側の触媒層は45〜55重量%の希土類元素の含有量を有する、1に記載の陰極。
[3]
前記少なくとも一つの希土類元素はプラセオジムである、請求項1または2に記載の陰極。
[4]
前記触媒被覆はロジウムを含んでいない、1から3のいずれかに記載の陰極。
[5]
前記触媒被覆は銀を含んでいる、1から4のいずれかに記載の陰極。
[6]
前記貴金属成分に対するパラジウムと銀の合計の重量比は、これらの元素について0.5
〜2である、1から5のいずれかに記載の陰極。
[7]
Pdの少なくとも一つの塩、Prの少なくとも一つの塩、およびPtとRuのいずれかから選択される貴金属の少なくとも一つの塩を含む第一の先駆物質の溶液の多重被覆熱分解と、それに続く、Pdの少なくとも一つの塩、Prの少なくとも一つの塩、およびPtとRuのいずれかから選択される貴金属の少なくとも一つの塩を含む第二の先駆物質の溶液の多重被覆熱分解を含み、このとき前記第二の先駆物質の溶液は、金属全体の合計について、前記第一の先駆物質の溶液におけるPrのパーセント含有量よりも低いPrのパーセント含有量を有する、1から4のいずれかに記載の陰極の製造方法。
[8]
前記のPd、Pr、PtおよびRuの塩は硝酸塩であり、そして前記熱分解は430〜500℃の温度において行われる、7に記載の方法。
[9]
1から6のいずれかに記載の少なくとも一つの陰極を含む、アルカリ塩化物のブラインの電気分解のための電解槽。
Claims (9)
- 電解法のための陰極であって、金属基板と、この基板に設けられた少なくとも一つの内側の触媒層と一つの外側の触媒層とを含む多層の触媒被覆からなり、内側の触媒層と外側の触媒層の両者はパラジウム、少なくとも一つの希土類元素、および白金とルテニウムのいずれかから選択される少なくとも一つの貴金属成分を含み、このとき前記外側の触媒層は10〜45重量%の希土類元素の含有量を有し、そして前記内側の触媒層は前記外側の触媒層の前記含有量よりも高い希土類元素の含有量を有する、前記陰極。
- 前記外側の触媒層は30〜40重量%の希土類元素の含有量を有し、そして前記内側の触媒層は45〜55重量%の希土類元素の含有量を有する、請求項1に記載の陰極。
- 前記少なくとも一つの希土類元素はプラセオジムである、請求項1または2に記載の陰極。
- 前記触媒被覆はロジウムを含んでいない、請求項1から3のいずれかに記載の陰極。
- 前記触媒被覆は銀を含んでいる、請求項1から4のいずれかに記載の陰極。
- パラジウムの含有量が銀によってAg/Pdのモル比が0.15〜0.25であるよう
に部分的に置き換えられており、そして前記貴金属成分に対するパラジウムと銀の合計の重量比は、パラジウム、銀及び前記貴金属成分の元素について0.5〜2である、請求項
1から5のいずれかに記載の陰極。 - Pdの少なくとも一つの塩、Prの少なくとも一つの塩、およびPtとRuのいずれかから選択される貴金属の少なくとも一つの塩を含む第一の先駆物質の溶液の多重被覆熱分解と、それに続く、Pdの少なくとも一つの塩、Prの少なくとも一つの塩、およびPtとRuのいずれかから選択される貴金属の少なくとも一つの塩を含む第二の先駆物質の溶液の多重被覆熱分解を含み、このとき前記第二の先駆物質の溶液は、金属全体の合計につ
いて、前記第一の先駆物質の溶液におけるPrのパーセント含有量よりも低いPrのパーセント含有量を有する、請求項1から4のいずれかに記載の陰極の製造方法。 - 前記のPd、Pr、PtおよびRuの塩は硝酸塩であり、そして前記第一の先駆物質の溶液の多重被覆熱分解及び前記第二の先駆物質の溶液の多重被覆熱分解は430〜500℃の温度において行われる、請求項7に記載の方法。
- 請求項1から6のいずれかに記載の少なくとも一つの陰極を含む、クロロアルカリ電解槽。
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