EP1608795B1 - Method for the formation of a coating of metal oxides on an electrically-conducting substrate, resultant activated cathode and use thereof for the electrolysis of aqueous solutions of alkaline metal chlorides - Google Patents
Method for the formation of a coating of metal oxides on an electrically-conducting substrate, resultant activated cathode and use thereof for the electrolysis of aqueous solutions of alkaline metal chlorides Download PDFInfo
- Publication number
- EP1608795B1 EP1608795B1 EP04742353A EP04742353A EP1608795B1 EP 1608795 B1 EP1608795 B1 EP 1608795B1 EP 04742353 A EP04742353 A EP 04742353A EP 04742353 A EP04742353 A EP 04742353A EP 1608795 B1 EP1608795 B1 EP 1608795B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- process according
- substrate
- cathode
- acetylacetonate
- 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.)
- Expired - Lifetime
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- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 4
- 229910001510 metal chloride Inorganic materials 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052742 iron Inorganic materials 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 41
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 28
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 27
- 239000010959 steel Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010970 precious metal Substances 0.000 claims abstract description 12
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- -1 alkali metal chlorates Chemical class 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 230000010287 polarization Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 7
- 238000002848 electrochemical method Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- ADVORQMAWLEPOI-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxotitanium Chemical compound [Ti]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O ADVORQMAWLEPOI-XHTSQIMGSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- 229910001902 chlorine oxide Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/04—Pretreatment of the material to be coated
-
- 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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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/08—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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- C—CHEMISTRY; METALLURGY
- 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
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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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
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- C—CHEMISTRY; METALLURGY
- 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
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
Definitions
- the invention relates to a method for forming a coating of metal oxides comprising at least one precious metal of group VIII of the periodic table of elements possibly associated with titanium and / or zirconium, on an electroconductive substrate.
- the invention also relates to an activated cathode obtained from the electroconductive substrate coated according to the method of the invention.
- the invention also relates to the use of said activated cathode, in particular for the electrolysis of aqueous solutions of alkali metal chlorides and particularly for the preparation of chlorine and sodium hydroxide as well as for the preparation of sodium chlorate.
- chlorine and sodium hydroxide as well as sodium chlorate
- electrolytic cells each of which comprises a plurality of steel cathodes and a plurality of titanium anodes coated with a mixture of titanium oxides. and ruthenium.
- electrolytic solution consisting of about 200 to 300 g / l of sodium chloride.
- sodium chlorate they generally contain 50 to 250 g / l of sodium chloride.
- overvoltage is meant the difference between the thermodynamic potential of the redox couple concerned (H 2 0 / H 2 ) with respect to a reference cathode and the potential actually measured in the medium concerned, with respect to the same reference electrode.
- overvoltage we use the term overvoltage to designate the absolute value of the cathode overvoltage.
- a cathode whose substrate is a plate of titanium, zirconium, niobium or alloy essentially consisting of a combination of these metals and on which is applied an oxide layer metal, essentially consisting of an oxide of one or a plurality of metals selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and optionally an oxide of one or more metals selected from calcium, magnesium, strontium, barium, zinc, chromium, molybdenum, tungsten, selenium and tellurium.
- a cathode consisting of an electrically conductive substrate of nickel, stainless steel or mild steel with a coating consisting of a plurality of layers of metal oxides, the surface layer consisting of by a valve metal oxide, that is to say a metal selected from the groups 4b, 5b and 6b of the periodic table of the elements and the intermediate layer consisting of a precious metal oxide of the group VIII, it is that is, ruthenium, rhodium, palladium, osmium, iridium and platinum.
- the intermediate and superficial layers can be constituted by the oxide of the only metal concerned or by a mixed oxide of the metal in question and the second metal in a small proportion.
- an activated cathode constituted by an electroconductive substrate, either titanium or nickel, coated with an intermediate layer of titanium-based oxides and a precious metal of the group VIII of the Periodic Table of Elements and an outer layer of metal oxides comprising titanium, zirconium and a precious metal of group VIII of the Periodic Table of Elements; said coating being obtained by thermal decomposition of a solution of chloride or oxychloride of these metals in ethanol or isopropanol.
- the Applicant has found that by judiciously choosing organometallic compounds and their solvents, it obtained coatings of the aforementioned metal oxides having a very good adhesion to substrates made of steel or iron.
- the subject of the invention is therefore a process for forming a coating of metal oxides comprising at least one precious metal of group VIII of the periodic table of elements possibly associated with titanium and / or zirconium, on an electroconductive substrate, said method consisting in applying to said substrate a solution comprising at least one organometallic compound and then converting said (or said) organometallic compound (s) into metal oxide (s) by means of a heat treatment; said method being characterized in that the electroconductive substrate is of steel or iron and in that the only solution applied to said substrate is a non-aqueous solution of metallic acetylacetonate or a mixture of dissolved metal acetylacetonates ( ) in a solvent (s) specifically solubilizing each metal acetylacetonate, the solvent (s) being chosen from alcohols, ketones, chloromethanes or a mixture of two or more solvents mentioned above .
- precious metal of Group VIII of the Periodic Table of Elements is currently ruthenium, rhodium, palladium, osmium, iridium or platinum.
- ruthenium or iridium and especially ruthenium will be used.
- ketones used according to the present invention include acetone, methyl ethyl ketone.
- chloromethanes that may be used according to the present invention, mention may be made of methylene chloride or chloroform.
- the solution that is applied to the electroconductive substrate is a solution of an acetylacetonate of a metal selected from the group: Ru, Rh, Pd, Os, Ir, Pt, Ti and Zr or a mixture of acetylacetonates of two or more of the metals included in this group.
- said solution contains only a metallic acetylacetonate, it can be obtained by dissolving this metal acetylacetonate in its specific solvent, or in a solvent mixture containing the specific solvent.
- the solution can be advantageously carried out with stirring at room temperature, or at a slightly higher temperature to improve the dissolution of metal acetylacetonates.
- concentrated solutions of metal acetylacetonates are preferably used and, in order to prepare said solutions, it is for the person skilled in the art to take into account the solubility of the various metal acetylacetonates in the solvents (or mixture of solvents). usable according to the present invention.
- a preferred method of forming a metal oxide coating according to the present invention is, in a first step, to pretreat the steel or iron substrate to impart roughness characteristics to the surface and then, in a second step depositing on said pretreated substrate the solution containing the metal acetylacetonate (s) prepared as indicated above; then to dry and calcine the substrate thus coated.
- This second step - impregnation / drying / calcination - can be advantageously repeated one or more times to obtain the coating.
- this second step is repeated until a desired metal mass is obtained.
- this step is repeated between 2 and 6 times.
- the pretreatment generally consists of subjecting the substrate to sandblasting, followed optionally by acid washing, or to etching with an aqueous solution of oxalic acid, hydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, a mixture of hydrofluoric acid and glycerol, a mixture of hydrofluoric acid, nitric acid and glycerol or a mixture of hydrofluoric acid, nitric acid and hydrogen peroxide, followed by one or more washing (s) with degassed demineralised water.
- the substrate may be in the form of a solid plate, perforated plate, expanded metal or cathode basket made from the expanded or perforated metal.
- the solution can be deposited on the pretreated substrate using various techniques such as sol-gel, spraying or coating.
- the pretreated substrate is coated with the solution, for example with the aid of a brush.
- the substrate thus coated is then dried in air and / or in an oven at a temperature at most equal to 150 ° C.
- the substrate is calcined under air or under inert gas enriched with oxygen at a temperature of at least 300 ° C and preferably between 400 ° C and 600 ° C for a period of 10 minutes to 2 hours.
- This method of operation makes it possible to convert the acetylacetonate (s) metal (s) into a coating of metal oxide (s) uniform and adherent on the substrate steel or iron.
- the solution can be deposited on one of the pretreated substrate faces as well as on both sides.
- the weight of precious metal deposited, expressed in g / m 2 relative to the geometrical surface of the substrate is at least equal to 2 g / m 2 , generally between 2 and 20 g / m 2 and preferably between 5 and 10 g / m 2 .
- the subject of the invention is also an so-called activated cathode obtained from an electroconductive substrate coated according to the invention.
- the cathode of the present invention is particularly suitable for the electrolysis of aqueous solutions of alkali metal chlorides and especially aqueous solutions of NaCl.
- cathode of the present invention in combination with an anode makes it possible to electrolytically synthesize the chlorine and hydroxide of an alkali metal.
- cathode of the present invention in combination with an anode makes it possible to electrolytically synthesize the chlorate of an alkali metal.
- DSA Dissionally Stable Anode
- anodes consist of a titanium substrate coated with a layer of titanium oxide and ruthenium.
- the ruthenium / titanium molar ratio in this layer is advantageously between 0.4 and 2.4.
- the cathode of the present invention has the advantage of having a low overvoltage and of being a cheap substrate.
- the coating solution is prepared by dissolving 0.653 g of ruthenium acetylacetonate, 0.329 g of titanyl acetylacetonate and 0.178 g of zirconium acetylacetonate in 10 ml of ethanol + 10 ml of acetone + 10 ml of chloroform. to obtain a molar distribution 45 Ru / 45 Ti / 10 Zr.
- the support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
- the substrate is sandblasted with Corundum and then rinsed with acetone.
- the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.4 g / m 2 . This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 7.9 g / m 2 , ie an equivalent weight of 3.3 g (Ru) / m 2 .
- the last heat treatment of the support is 30 minutes at 450 ° C.
- the steel rod Prior to the electrochemical evaluation, the steel rod is masked with Teflon tape to delineate a well-defined surface.
- the coated support is then placed in an electrochemical cell containing 200 ml of 1M sodium hydroxide at room temperature and will be tested in cathode.
- a counter electrode consisting of an RuO 2 -TiO 2 coated titanium anode and a saturated Calomel Reference Electrode (ECS) extended with a capillary containing a saturated KCl solution is used.
- ECS Calomel Reference Electrode
- the electrodes are connected to the terminals of a potentiostat (Solartron).
- the activity of the cathode is measured from the polarization curves (of the abandonment potential up to -1.3 or -1.4 V / ECS, at a speed of 1mV / s).
- An activation step is then carried out by applying a current of an intensity equal to 2 amperes to the cathode for 1 hour, and a new polarization curve is then drawn to evaluate the changes in the electrochemical performances of the cathode. This activation step is repeated until a stable polarization curve is obtained, that is to say identical to the curve preceding the last activation (generally 3 or 4 times).
- Table (1) below shows the evolution of the cathode potential for a current density of 1.6 kA / m 2 as a function of the number of activation steps.
- the voltage gain is the difference between the potential of the activated cathode and the potential of the bare iron cathode for the same current density (here 1.6 kA / m 2 ).
- the solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate and 0.329 g of titanyl acetylacetonate in 10 ml of ethanol + 10 ml of acetone so as to obtain an equimolar Ru / Ti solution.
- the support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
- the substrate is sandblasted with Corundum and then rinsed with acetone.
- the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.2 g / m 2 .
- This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 9.8 g / m 2 , ie an equivalent mass of 4.6 g (Ru) / m 2 .
- the last heat treatment is 30 minutes at 450 ° C.
- the solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate in 10 ml of ethanol + 10 ml of acetone.
- the support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
- the substrate is sandblasted with Corundum and then rinsed with acetone.
- the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 1.9 g / m 2 .
- This procedure is repeated twice (3 layers in total) so as to obtain a coating having a mass of 3.8 g / m 2 , ie an equivalent mass of 2.9 g (Ru) / m 2 .
- the last heat treatment is timed at 450 ° C.
- the solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate in 10 ml of ethanol.
- the support consists of a solid steel plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
- the substrate is sandblasted with Corundum and then rinsed with acetone.
- the support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.1 g / m 2 .
- This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 7.6 g / m 2 , ie an equivalent mass of 5.8 g (Ru) / m 2 .
- the last heat treatment is 30 minutes at 450 ° C.
- More than 25 activated cathodes having a 100% RuO 2 coating were prepared under conditions similar to those described in Examples 3 and 4, on solid supports made of iron or steel or on supports deployed in iron or steel, and characterized by the procedure described in Example 1.
- the average voltage gain found by comparison with a cathode of the same shape and of the same nature but uncoated is 200 ⁇ 50 mV.
- a 72 cm 2 activated cathode is prepared for a chlorine-soda electrolysis laboratory pilot diaphragm.
- the substrate consists of a steel mesh, used on industrial cells.
- the desired coating is of equimolar composition in Ru and Ti, it is prepared according to the procedure described in Example 2, it is deposited on both sides of the support material.
- the coating weight is 13.7 g / m 2 , ie 6.5 g (Ru) / m 2 , deposited in 4 layers. No electrochemical characterization is made on this cathode before its mounting on the pilot cell because of its size.
- the activated cathode is mounted in a pilot cell electrolysis chlorine-soda diaphragm using a diaphragm Polyramix® and operating continuously 24h / 24h, 7days / 7.
- a racking and feeding game keeps the concentration of the different products in the electrolysis cell constant.
- the operating conditions are as follows: 2.5 kA / m 2 , 85 ° C., sodium hydroxide concentration in the cathode liquor between 120 g / l and 140 g / l, expanded titanium anode coated with RuO 2 -TiO 2 .
- An uncoated iron cathode from the same industrial support is installed in an equivalent cell, operating with the same operating conditions.
- Graph (1) shows the evolution of the potential of these two cathodes over 120 days of operation.
- ⁇ denotes activated cathode and ⁇ denotes bare steel cathode.
- the gain in voltage, obtained by difference of the two potentials, is of the order of 180 mV over the period 20 days - 120 days of operation.
- a 200 cm 2 (5 cm ⁇ 40 cm) activated cathode is prepared for a sodium chlorate electrolysis pilot.
- An iron support is coated on these two faces with an equimolar deposit of Ru and Ti according to the procedure described in Example 2, except that the final heat treatment is 1 hour at 450 ° C.
- the deposit mass is 10.3 g / m 2 , 4.9 g (Ru) / m 2 .
- This cathode is then placed in a pilot cell of sodium chlorate electrolysis.
- the anode consists of an expanded titanium support coated RuO 2 -TiO 2 .
- the voltage of the cell using the activated cathode is 200 ⁇ 50 mV lower than the voltage of the cell using an uncoated iron cathode.
- a substrate consisting of a solid nickel plate and a substrate consisting of a solid iron plate are coated with an equimolar RuO 2 -TiO 2 deposit according to the procedure described in Example 2 by repeating the "coating" cycle. drying / calcination "until a deposit of 9 - 10 g / m 2 , ie 4.3 to 4.7 g (Ru) / m 2 is obtained. The last heat treatment is 30 minutes at 450 ° C. 3 layers are necessary for the iron support, 6 layers for the nickel support: the deposit is less adherent on nickel than on iron; these cathodes are then evaluated electrochemically according to the procedure described in Example 1.
- Graph (2) shows the polarization curves after stabilization of each of these cathodes.
- An equimolar coating solution Ru / Ti is prepared by dissolving 5.18 g of RuCl 3 , 1.5H 2 O and 3.1 ml of TiOCl 2 , 2HCl (124.5 g (Ti) / l) in 10 ml of absolute ethanol. The solution is stirred to allow the products to dissolve.
- a first support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 .
- the substrate is sandblasted with Corundum and then rinsed with acetone.
- a second support consists of a solid nickel plate (3.5 x 2.5 cm) on which is welded a nickel rod; the total surface is 33 cm 2 .
- the substrate is sandblasted with Corundum and then rinsed with acetone.
- Each support is then completely coated with the solution, placed in an oven at 120 ° C for 15 minutes, and then in an oven at 450 ° C for 15 minutes.
- the last heat treatment is 30 minutes at 450 ° C.
- Table (5) below shows the evolution of the mass of the deposit as a function of the number of cycles "coating / drying / calcination" for each of the two supports.
- ⁇ u> TABLE 5 ⁇ / u> Iron support Nickel support 1 st layer 14.1 g / m 2 6.2 g / m 2 2nd layer 25.8 g / m 2 12.4 g / m 2 3rd layer 18.5 g / m 2 4th layer 21.2 g / m 2 Deposit color Brown black
Abstract
Description
L'invention concerne un procédé de formation d'un revêtement d'oxydes métalliques comprenant au moins un métal précieux du groupe VIII de la classification périodique des éléments éventuellement associé à du titane et/ou du zirconium, sur un substrat électroconducteur.The invention relates to a method for forming a coating of metal oxides comprising at least one precious metal of group VIII of the periodic table of elements possibly associated with titanium and / or zirconium, on an electroconductive substrate.
L'invention se rapporte également à une cathode activée obtenue à partir du substrat électroconducteur revêtu selon le procédé de l'invention.The invention also relates to an activated cathode obtained from the electroconductive substrate coated according to the method of the invention.
L'invention concerne également l'utilisation de ladite cathode activée, notamment pour l'électrolyse de solutions aqueuses de chlorures de métaux alcalins et particulièrement pour la préparation du chlore et d'hydroxyde de sodium ainsi que pour la préparation du chlorate de sodium.The invention also relates to the use of said activated cathode, in particular for the electrolysis of aqueous solutions of alkali metal chlorides and particularly for the preparation of chlorine and sodium hydroxide as well as for the preparation of sodium chlorate.
Ainsi, industriellement le chlore et l'hydroxyde de sodium, ainsi que le chlorate de sodium, sont fabriqués dans des cellules électrolytiques, chacune d'elles comprenant plusieurs cathodes en acier et plusieurs anodes en titane revêtues d'un mélange d'oxydes de titane et de ruthénium. S'agissant de la préparation du chlore et de la soude, les cellules sont en général alimentées en solution électrolytique constituée d'environ 200 à 300 g/l de chlorure de sodium. Dans le cas de la synthèse du chlorate de sodium, elles contiennent en général 50 à 250 g/l de chlorure de sodium.Thus, industrially, chlorine and sodium hydroxide, as well as sodium chlorate, are manufactured in electrolytic cells, each of which comprises a plurality of steel cathodes and a plurality of titanium anodes coated with a mixture of titanium oxides. and ruthenium. As regards the preparation of chlorine and sodium hydroxide, the cells are generally fed with electrolytic solution consisting of about 200 to 300 g / l of sodium chloride. In the case of the synthesis of sodium chlorate, they generally contain 50 to 250 g / l of sodium chloride.
Cependant, ces cathodes en acier présentent une surtension relativement élevée en valeur absolue comme cathodes de réduction de l'eau et possèdent également une résistance à la corrosion par le chlore dissous insuffisante.However, these steel cathodes have a relatively high overvoltage in absolute value as cathodes of water reduction and also have a resistance to corrosion by insufficient dissolved chlorine.
Par surtension, on entend l'écart entre le potentiel thermodynamique du couple redox concerné (H20/H2) par rapport à une cathode de référence et le potentiel effectivement mesuré dans le milieu concerné, par rapport à la même électrode de référence. Par convention on utilisera le terme surtension pour désigner la valeur absolue de la surtension cathodique.By overvoltage is meant the difference between the thermodynamic potential of the redox couple concerned (
Afin de surmonter ces inconvénients, il a été proposé de nombreuses cathodes.In order to overcome these disadvantages, many cathodes have been proposed.
Ainsi, dans la demande de brevet français FR 2311108, on décrit une cathode dont le substrat est une plaque en titane, en zirconium, en niobium ou en alliage essentiellement constitué par une association de ces métaux et sur lequel est appliquée une couche d'oxyde métallique, essentiellement constituée par un oxyde d'un ou plusieurs métaux choisis parmi le ruthénium, le rhodium, le palladium, l'osmium, l'iridium et le platine et éventuellement un oxyde d'un ou plusieurs métaux choisis parmi le calcium, le magnésium, le strontium, le baryum, le zinc, le chrome, le molybdène, le tungstène, le sélénium et le tellure.Thus, in the French patent application FR 2311108, there is described a cathode whose substrate is a plate of titanium, zirconium, niobium or alloy essentially consisting of a combination of these metals and on which is applied an oxide layer metal, essentially consisting of an oxide of one or a plurality of metals selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and optionally an oxide of one or more metals selected from calcium, magnesium, strontium, barium, zinc, chromium, molybdenum, tungsten, selenium and tellurium.
Le brevet américain US 4,100,049 décrit une cathode comprenant un substrat en fer, nickel, cobalt ou en alliage de ces métaux et un revêtement d'oxyde de palladium et d'oxyde de zirconium.US Pat. No. 4,100,049 describes a cathode comprising a substrate of iron, nickel, cobalt or an alloy of these metals and a coating of palladium oxide and zirconium oxide.
Dans la demande de brevet européen EP 209427, on propose une cathode constituée d'un substrat électriquement conducteur en nickel, en acier inoxydable ou en acier doux portant un revêtement constitué d'une pluralité de couches d'oxydes métalliques, la couche superficielle étant constituée par un oxyde de métal valve, c'est-à-dire un métal choisi dans les groupes 4b, 5b et 6b de la classification périodique des éléments et la couche intermédiaire étant constituée par un oxyde de métal précieux du groupe VIII, c'est-à-dire ruthénium, rhodium, palladium, osmium, iridium et platine.In the European patent application EP 209427, there is provided a cathode consisting of an electrically conductive substrate of nickel, stainless steel or mild steel with a coating consisting of a plurality of layers of metal oxides, the surface layer consisting of by a valve metal oxide, that is to say a metal selected from the groups 4b, 5b and 6b of the periodic table of the elements and the intermediate layer consisting of a precious metal oxide of the group VIII, it is that is, ruthenium, rhodium, palladium, osmium, iridium and platinum.
Les couches intermédiaires et superficielles peuvent être constituées par l'oxyde du seul métal concerné ou par un oxyde mixte du métal concerné et du second métal en faible proportion.The intermediate and superficial layers can be constituted by the oxide of the only metal concerned or by a mixed oxide of the metal in question and the second metal in a small proportion.
Dans la demande de brevet FR 2797646, la demanderesse a proposé une cathode activé constituée par un substrat électroconducteur, soit en titane, soit en nickel, revêtu d'une couche intermédiaire d'oxydes à base de titane et d'un métal précieux du groupe VIII de la classification périodique des éléments et d'une couche externe d'oxydes métalliques comprenant du titane, du zirconium et un métal précieux du groupe VIII de la classification périodique des éléments ; ledit revêtement étant obtenu par décomposition thermique d'une solution de chlorure ou d'oxychlorure de ces métaux dans l'éthanol ou l'isopropanol.In the patent application FR 2797646, the Applicant has proposed an activated cathode constituted by an electroconductive substrate, either titanium or nickel, coated with an intermediate layer of titanium-based oxides and a precious metal of the group VIII of the Periodic Table of Elements and an outer layer of metal oxides comprising titanium, zirconium and a precious metal of group VIII of the Periodic Table of Elements; said coating being obtained by thermal decomposition of a solution of chloride or oxychloride of these metals in ethanol or isopropanol.
Dans un souci d'économie, il est de plus en plus souhaité d'utiliser des substrats moins coûteux tels que des substrats en acier ou en fer.For the sake of economy, it is increasingly desired to use less expensive substrates such as steel or iron substrates.
Cependant, la demanderesse a constaté que la méthode précédemment mentionnée ne permettait pas d'obtenir un revêtement adhérent sur un substrat électroconducteur en acier ou en fer.However, the Applicant has found that the previously mentioned method does not allow to obtain an adherent coating on an electroconductive substrate steel or iron.
La demanderesse a trouvé qu'en choisissant judicieusement des composés organométalliques et leurs solvants, elle obtenait des revêtements des oxydes métalliques précédemment mentionnés présentant une très bonne adhérence sur des substrats en acier ou en fer.The Applicant has found that by judiciously choosing organometallic compounds and their solvents, it obtained coatings of the aforementioned metal oxides having a very good adhesion to substrates made of steel or iron.
L'invention a donc pour objet un procédé de formation d'un revêtement d'oxydes métalliques comprenant au moins un métal précieux du groupe VIII de la classification périodique des éléments éventuellement associé à du titane et/ou du zirconium, sur un substrat électroconducteur, ledit procédé consistant à appliquer sur ledit substrat une solution comprenant au moins un composé organométallique puis à transformer ledit (ou lesdits) composé(s) organométallique(s) en oxyde(s) métallique(s) au moyen d'un traitement thermique ; ledit procédé étant caractérisé en ce que le substrat électroconducteur est en acier ou en fer et en ce que la seule solution appliquée sur ledit substrat est une solution, non aqueuse, d'acétylacétonate métallique ou d'un mélange d'acétylacétonates métalliques dissout(s) dans un (des) solvant(s) solubilisant spécifiquement chaque acétylacétonate métallique, le (les) solvant(s) étant choisi(s) parmi les alcools, les cétones, les chlorométhanes ou un mélange de deux ou plusieurs solvants ci-dessus mentionnés.The subject of the invention is therefore a process for forming a coating of metal oxides comprising at least one precious metal of group VIII of the periodic table of elements possibly associated with titanium and / or zirconium, on an electroconductive substrate, said method consisting in applying to said substrate a solution comprising at least one organometallic compound and then converting said (or said) organometallic compound (s) into metal oxide (s) by means of a heat treatment; said method being characterized in that the electroconductive substrate is of steel or iron and in that the only solution applied to said substrate is a non-aqueous solution of metallic acetylacetonate or a mixture of dissolved metal acetylacetonates ( ) in a solvent (s) specifically solubilizing each metal acetylacetonate, the solvent (s) being chosen from alcohols, ketones, chloromethanes or a mixture of two or more solvents mentioned above .
Selon la présente invention, par métal précieux du groupe VIII de la classification périodique des éléments, on entend présentement le ruthénium, le rhodium, le palladium, l'osmium, l'iridium ou le platine. De préférence, on utilisera le ruthénium ou l'iridium et, tout particulièrement le ruthénium.According to the present invention, precious metal of Group VIII of the Periodic Table of Elements is currently ruthenium, rhodium, palladium, osmium, iridium or platinum. Preferably, ruthenium or iridium and especially ruthenium will be used.
A titre d'illustration d'alcools utilisables selon la présente invention, on citera l'éthanol, l'isopropanol.By way of illustration of alcohols which can be used according to the present invention, mention may be made of ethanol and isopropanol.
A titre d'illustration de cétones utilisables selon la présente invention, on citera l'acétone, la méthyléthylcétone.Illustrative ketones used according to the present invention include acetone, methyl ethyl ketone.
A titre d'illustration de chlorométhanes utilisables selon la présente invention, on citera le chlorure de méthylène, le chloroforme.By way of illustration of chloromethanes that may be used according to the present invention, mention may be made of methylene chloride or chloroform.
Selon la présente invention, la solution qui est appliquée sur le substrat électroconducteur est une solution d'un acétylacétonate d'un métal choisi dans le groupe : Ru, Rh, Pd, Os, Ir, Pt, Ti et Zr ou encore un mélange d'acétylacétonates de deux ou plusieurs des métaux repris dans ce groupe.According to the present invention, the solution that is applied to the electroconductive substrate is a solution of an acetylacetonate of a metal selected from the group: Ru, Rh, Pd, Os, Ir, Pt, Ti and Zr or a mixture of acetylacetonates of two or more of the metals included in this group.
Plusieurs cas de figures sont possibles pour préparer la solution d'acétylacétonate(s) métallique(s) servant au revêtement du substrat électroconducteur selon le procédé de l'invention.Several scenarios are possible to prepare the acetylacetonate solution (s) metal (s) for coating the electroconductive substrate according to the method of the invention.
Si ladite solution ne contient qu'un acétylacétonate métallique, elle peut être obtenue par dissolution de cet acétylacétonate métallique dans son solvant spécifique, ou dans un mélange de solvants contenant le solvant spécifique.If said solution contains only a metallic acetylacetonate, it can be obtained by dissolving this metal acetylacetonate in its specific solvent, or in a solvent mixture containing the specific solvent.
Si ladite solution contient plusieurs acétylacétonates métalliques, elle peut être obtenue :
- soit par dissolution desdits acétylacétonates métalliques dans un mélange de solvants contenant les solvants spécifiques desdits acétylacétonates métalliques ;
- soit par mélange de solutions ne contenant qu'un seul acétylacétonate métallique obtenues par dissolution dudit acétylacétonate métallique dans un solvant spécifique ou dans un mélange de solvants contenant le solvant spécifique dudit acétylacétonate.
- or by dissolving said metal acetylacetonates in a solvent mixture containing the specific solvents of said metal acetylacetonates;
- or by mixing solutions containing only one metallic acetylacetonate obtained by dissolving said metallic acetylacetonate in a solvent specific or in a solvent mixture containing the specific solvent of said acetylacetonate.
La solution peut être avantageusement réalisée sous agitation, à température ambiante, voir à une température légèrement supérieure pour améliorer la dissolution des acétylacétonates métalliques.The solution can be advantageously carried out with stirring at room temperature, or at a slightly higher temperature to improve the dissolution of metal acetylacetonates.
Selon la présente invention, on utilisera de préférence des solutions concentrées d'acétylacétonates métalliques et, pour préparer lesdites solutions, il appartient à l'homme du métier de prendre en compte la solubilité des divers acétylacétonates métalliques dans les solvants (ou mélange de solvants) utilisables selon la présente invention.According to the present invention, concentrated solutions of metal acetylacetonates are preferably used and, in order to prepare said solutions, it is for the person skilled in the art to take into account the solubility of the various metal acetylacetonates in the solvents (or mixture of solvents). usable according to the present invention.
Par exemple, on utilisera, à température ambiante, une solution éthanolique d'acétylacétonate de ruthénium - (C5H7O2)3Ru- à 0,25 mole/litre et une solution acétonique d'acétylacétonate de titanyle - (C5H7O2)2TiO - à 0,8 mole/litre.For example, at room temperature, an ethanolic solution of ruthenium acetylacetonate - (C 5 H 7 O 2 ) 3 R - at 0.25 mol / liter and an acetonic solution of titanyl acetylacetonate - (C 5 H 7 O 2 ) 2 TiO 2 at 0.8 mole / liter.
Un mode préféré de formation d'un revêtement d'oxydes métalliques selon la présente invention consiste, dans une première étape, à prétraiter le substrat en acier ou en fer pour lui conférer des caractéristiques de rugosité à la surface, puis, dans une seconde étape à déposer sur ledit substrat prétraité la solution contenant le (ou les) acétylacétonate(s) métallique(s) préparée comme indiqué précédemment ; puis à sécher et à calciner le substrat ainsi revêtu.A preferred method of forming a metal oxide coating according to the present invention is, in a first step, to pretreat the steel or iron substrate to impart roughness characteristics to the surface and then, in a second step depositing on said pretreated substrate the solution containing the metal acetylacetonate (s) prepared as indicated above; then to dry and calcine the substrate thus coated.
Cette seconde étape - imprégnation / séchage / calcination - peut être avantageusement répétée une ou plusieurs fois pour obtenir le revêtement. De préférence, cette seconde étape est répétée jusqu'à obtention d'une masse métallique souhaitée. Généralement, cette étape est répétée entre 2 et 6 fois.This second step - impregnation / drying / calcination - can be advantageously repeated one or more times to obtain the coating. Preferably, this second step is repeated until a desired metal mass is obtained. Generally, this step is repeated between 2 and 6 times.
Le prétraitement consiste en général à soumettre le substrat, soit à un sablage suivi éventuellement d'un lavage à l'acide, soit à un décapage à l'aide d'une solution aqueuse d'acide oxalique, d'acide fluorhydrique, d'un mélange d'acide fluorhydrique et d'acide nitrique, d'un mélange d'acide fluorhydrique et de glycérol, d'un mélange d'acide fluorhydrique, d'acide nitrique et de glycérol ou d'un mélange d'acide fluorhydrique, d'acide nitrique et de peroxyde d'hydrogène, suivi d'un ou de plusieurs lavage(s) à l'eau déminéralisée dégazéifiée.The pretreatment generally consists of subjecting the substrate to sandblasting, followed optionally by acid washing, or to etching with an aqueous solution of oxalic acid, hydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, a mixture of hydrofluoric acid and glycerol, a mixture of hydrofluoric acid, nitric acid and glycerol or a mixture of hydrofluoric acid, nitric acid and hydrogen peroxide, followed by one or more washing (s) with degassed demineralised water.
Le substrat peut être sous forme de plaque massive, plaque perforée, métal déployé ou panier cathodique constitué à partir du métal déployé ou perforé.The substrate may be in the form of a solid plate, perforated plate, expanded metal or cathode basket made from the expanded or perforated metal.
On peut déposer la solution sur le substrat prétraité en utilisant différentes techniques telles que sol-gel, pulvérisation ou enduction. Avantageusement on enduit le substrat prétraité avec la solution, par exemple à l'aide d'un pinceau. Le substrat ainsi revêtu est ensuite séché à l'air et/ou dans une étuve à une température au plus égale à 150°C. Après le séchage, le substrat est calciné sous air ou bien encore sous gaz inerte enrichi avec de l'oxygène à une température au moins égale à 300°C et, de préférence, comprise entre 400°C et 600°C pendant une durée allant de 10 minutes à 2 heures.The solution can be deposited on the pretreated substrate using various techniques such as sol-gel, spraying or coating. Advantageously, the pretreated substrate is coated with the solution, for example with the aid of a brush. The substrate thus coated is then dried in air and / or in an oven at a temperature at most equal to 150 ° C. After drying, the substrate is calcined under air or under inert gas enriched with oxygen at a temperature of at least 300 ° C and preferably between 400 ° C and 600 ° C for a period of 10 minutes to 2 hours.
Cette façon d'opérer permet de transformer le(s) acétylacétonate(s) métallique(s) en un revêtement d'oxyde(s) métallique(s) uniforme et adhérent sur le substrat en acier ou en fer.This method of operation makes it possible to convert the acetylacetonate (s) metal (s) into a coating of metal oxide (s) uniform and adherent on the substrate steel or iron.
On peut déposer la solution aussi bien sur l'une des faces de substrat prétraité que sur les deux faces.The solution can be deposited on one of the pretreated substrate faces as well as on both sides.
La masse pondérale de métal précieux déposée, exprimée en g/m2 rapportée à la surface géométrique du substrat est au moins égale à 2 g/m2, généralement comprise entre 2 et 20 g/m2 et préférentiellement comprise entre 5 et 10 g/m2.The weight of precious metal deposited, expressed in g / m 2 relative to the geometrical surface of the substrate is at least equal to 2 g / m 2 , generally between 2 and 20 g / m 2 and preferably between 5 and 10 g / m 2 .
L'invention a également pour objet une cathode dite activée obtenue à partir d'un substrat électroconducteur revêtu selon l'invention.The subject of the invention is also an so-called activated cathode obtained from an electroconductive substrate coated according to the invention.
La cathode de la présente invention convient tout particulièrement à l'électrolyse de solutions aqueuses de chlorures de métaux alcalins et notamment de solutions aqueuses de NaCl.The cathode of the present invention is particularly suitable for the electrolysis of aqueous solutions of alkali metal chlorides and especially aqueous solutions of NaCl.
L'utilisation de la cathode de la présente invention en association avec une anode permet de synthétiser électrolytiquement le chlore et l'hydroxyde d'un métal alcalin.The use of the cathode of the present invention in combination with an anode makes it possible to electrolytically synthesize the chlorine and hydroxide of an alkali metal.
L'utilisation de la cathode de la présente invention en association avec une anode permet de synthétiser électrolytiquement le chlorate d'un métal alcalin.The use of the cathode of the present invention in combination with an anode makes it possible to electrolytically synthesize the chlorate of an alkali metal.
On peut citer comme anode, les anodes DSA (Dimensionally Stable Anode) constituées d'un substrat en titane revêtu d'une couche d'oxydes de titane et de ruthénium. Le rapport molaire ruthénium /titane dans cette couche est avantageusement compris entre 0,4 et 2,4.As anode, DSA (Dimensionally Stable Anode) anodes consist of a titanium substrate coated with a layer of titanium oxide and ruthenium. The ruthenium / titanium molar ratio in this layer is advantageously between 0.4 and 2.4.
La cathode de la présente invention possède l'avantage d'avoir une surtension faible et d'être constituée d'un substrat bon marché.The cathode of the present invention has the advantage of having a low overvoltage and of being a cheap substrate.
Les exemples qui suivent illustrent l'invention.The following examples illustrate the invention.
La solution d'enduction est préparée par dissolution de 0,653 g d'acétylacétonate de ruthénium, 0,329 g d'acétylacétonate de titanyle et 0,178 g d'acétylacétonate de zirconium dans 10 ml d'éthanol + 10 ml d'acétone + 10 ml de chloroforme pour obtenir une répartition molaire 45 Ru / 45 Ti / 10 Zr.The coating solution is prepared by dissolving 0.653 g of ruthenium acetylacetonate, 0.329 g of titanyl acetylacetonate and 0.178 g of zirconium acetylacetonate in 10 ml of ethanol + 10 ml of acetone + 10 ml of chloroform. to obtain a molar distribution 45 Ru / 45 Ti / 10 Zr.
Le support est constitué d'une plaque pleine en fer (3,5 x 2,5 cm) sur laquelle est soudée une tige en acier ; la surface totale est de 33 cm2. Le support est préalablement sablé avec du Corindon puis rincé avec de l'acétone.The support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 . The substrate is sandblasted with Corundum and then rinsed with acetone.
Le support est ensuite enduit dans sa totalité avec la solution, placé dans une étuve à 120°C pendant 15 minutes, puis dans un four à 450°C pendant 15 minutes. On obtient ainsi un revêtement de 2,4 g/m2. Cette procédure est répétée 3 fois (4 couches au total) de façon à obtenir un revêtement ayant une masse de 7,9 g/m2, soit une masse équivalente de 3,3 g(Ru)/m2. Le dernier traitement thermique du support est 30 minutes à 450°C.The support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.4 g / m 2 . This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 7.9 g / m 2 , ie an equivalent weight of 3.3 g (Ru) / m 2 . The last heat treatment of the support is 30 minutes at 450 ° C.
Avant l'évaluation électrochimique, la tige en acier est masquée avec du ruban Teflon pour délimiter une surface bien définie. Le support revêtu est ensuite placé dans une cellule électrochimique contenant 200 ml de soude 1M, à température ambiante et sera testé en cathode. On utilise une contre électrode constituée d'une anode de titane revêtu RuO2-TiO2, et une électrode de référence au Calomel Saturé (ECS) prolongée d'un capillaire contenant une solution saturée de KCl. Les électrodes sont connectées aux bornes d'un potentiostat (Solartron). L'activité de la cathode est mesurée à partir des courbes de polarisation (du potentiel d'abandon jusqu'à -1,3 ou - 1,4 V/ECS, à une vitesse de 1mV/s). On réalise ensuite une étape d'activation en appliquant un courant d'une intensité égale à 2 ampères à la cathode pendant 1 heure, et l'on trace ensuite une nouvelle courbe de polarisation pour évaluer les modifications des performances électrochimiques de la cathode. Cette étape d'activation est reproduite jusqu'à obtenir une courbe de polarisation stable, c'est-à-dire identique à la courbe précédant la dernière activation (en général 3 ou 4 fois).Prior to the electrochemical evaluation, the steel rod is masked with Teflon tape to delineate a well-defined surface. The coated support is then placed in an electrochemical cell containing 200 ml of 1M sodium hydroxide at room temperature and will be tested in cathode. A counter electrode consisting of an RuO 2 -TiO 2 coated titanium anode and a saturated Calomel Reference Electrode (ECS) extended with a capillary containing a saturated KCl solution is used. The electrodes are connected to the terminals of a potentiostat (Solartron). The activity of the cathode is measured from the polarization curves (of the abandonment potential up to -1.3 or -1.4 V / ECS, at a speed of 1mV / s). An activation step is then carried out by applying a current of an intensity equal to 2 amperes to the cathode for 1 hour, and a new polarization curve is then drawn to evaluate the changes in the electrochemical performances of the cathode. This activation step is repeated until a stable polarization curve is obtained, that is to say identical to the curve preceding the last activation (generally 3 or 4 times).
Le tableau (1) ci-dessous présente l'évolution du potentiel cathodique pour une densité de courant de 1,6 kA/m2 en fonction du nombre d'étapes d'activation. Moins le potentiel est négatif et plus la surtension de réduction de l'eau est faible, ce qui signifie plus la cathode est activée. En parallèle; les mêmes procédures de caractérisation sont appliquées sur un support de forme et nature identiques mais vierge de tout dépôt. Le gain en tension est l'écart entre le potentiel de la cathode activée et le potentiel de la cathode en fer nu pour une même densité de courant (ici 1,6 kA/m2).
La solution est préparée par dissolution de 0,500 g d'acétylacétonate de ruthénium et 0,329 g d'acétylacétonate de titanyle dans 10 ml d'éthanol + 10 ml d'acétone de façon à obtenir une solution équimolaire Ru /Ti.The solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate and 0.329 g of titanyl acetylacetonate in 10 ml of ethanol + 10 ml of acetone so as to obtain an equimolar Ru / Ti solution.
Le support est constitué d'une plaque pleine en fer (3,5 x 2,5 cm) sur laquelle est soudée une tige en acier; la surface totale est de 33 cm2. Le support est préalablement sablé avec du Corindon puis rincé avec de l'acétone.The support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 . The substrate is sandblasted with Corundum and then rinsed with acetone.
Le support est ensuite enduit dans sa totalité avec la solution, placé dans une étuve à 120°C pendant 15 minutes, puis dans un four à 450°C pendant 15 minutes. On obtient ainsi un revêtement de 2,2 g/m2. Cette procédure est répétée 3 fois (4 couches au total) de façon à obtenir un revêtement ayant une masse de 9,8 g/m2, soit une masse équivalente de 4,6 g(Ru)/m2. Le dernier traitement thermique est 30 minutes à 450°C.The support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.2 g / m 2 . This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 9.8 g / m 2 , ie an equivalent mass of 4.6 g (Ru) / m 2 . The last heat treatment is 30 minutes at 450 ° C.
La caractérisation électrochimique de cet élément est réalisée dans les mêmes conditions que celles décrites dans l'exemple 1. Le tableau (2) ci-dessous présente l'évolution du potentiel de la cathode et du gain en tension par comparaison avec une cathode en fer nu.
Plus de 25 cathodes activées ayant un revêtement équimolaire en Ru et Ti ont été préparées dans des conditions proches de celles-ci, sur des supports pleins en fer ou en acier ou sur des supports déployés en fer ou en acier et caractérisées selon le mode opératoire décrit dans l'exemple 1. Le gain en tension moyen constaté par comparaison avec une cathode de même forme et même nature non revêtue est de 160 ± 20 mV.More than 25 activated cathodes having an equimolar coating of Ru and Ti were prepared under conditions close to them, on solid supports made of iron or steel or on supports deployed in iron or steel and characterized according to the operating procedure. described in Example 1. The average voltage gain found by comparison with a cathode of the same shape and same uncoated nature is 160 ± 20 mV.
La solution est préparée par dissolution de 0,500 g d'acétylacétonate de ruthénium dans 10 ml d'éthanol + 10 ml d'acétone.The solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate in 10 ml of ethanol + 10 ml of acetone.
Le support est constitué d'une plaque pleine en fer (3,5 x 2,5 cm) sur laquelle est soudée une tige en acier; la surface totale est de 33 cm2. Le support est préalablement sablé avec du Corindon puis rincé avec de l'acétone.The support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 . The substrate is sandblasted with Corundum and then rinsed with acetone.
Le support est ensuite enduit dans sa totalité avec la solution, placé dans une étuve à 120°C pendant 15 minutes, puis dans un four à 450°C pendant 15 minutes. On obtient ainsi un revêtement de 1,9 g/m2. Cette procédure est répétée 2 fois (3 couches au total) de façon à obtenir un revêtement ayant une masse de 3,8 g/m2, soit une masse équivalente de 2,9 g(Ru)/m2. Le dernier traitement thermique est 30 minutés à 450°C.The support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 1.9 g / m 2 . This procedure is repeated twice (3 layers in total) so as to obtain a coating having a mass of 3.8 g / m 2 , ie an equivalent mass of 2.9 g (Ru) / m 2 . The last heat treatment is timed at 450 ° C.
La caractérisation électrochimique de l'élément est réalisée dans les mêmes conditions que celles décrites dans l'exemple 1. Le tableau (3) ci-dessous présente l'évolution du potentiel de la cathode et du gain en tension par comparaison avec une cathode en fer nu.
La solution est préparée par dissolution de 0,500 g d'acétylacétonate de ruthénium dans 10 ml d'éthanol.The solution is prepared by dissolving 0.500 g of ruthenium acetylacetonate in 10 ml of ethanol.
Le support est constitué d'une plaque pleine en acier (3,5 x 2,5 cm) sur laquelle est soudée une tige en acier; la surface totale est de 33 cm2. Le support est préalablement sablé avec du Corindon puis rincé avec de l'acétone.The support consists of a solid steel plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 . The substrate is sandblasted with Corundum and then rinsed with acetone.
Le support est ensuite enduit dans sa totalité avec la solution, placé dans une étuve à 120°C pendant 15 minutes, puis dans un four à 450°C pendant 15 minutes. On obtient ainsi un revêtement de 2,1 g/m2. Cette procédure est répétée 3 fois (4 couches au total) de façon à obtenir un revêtement ayant une masse de 7,6 g/m2, soit une masse équivalente de 5,8 g(Ru)/m2. Le dernier traitement thermique est de 30 minutes à 450°C.The support is then completely coated with the solution, placed in an oven at 120 ° C. for 15 minutes and then in an oven at 450 ° C. for 15 minutes. This gives a coating of 2.1 g / m 2 . This procedure is repeated 3 times (4 layers in total) so as to obtain a coating having a mass of 7.6 g / m 2 , ie an equivalent mass of 5.8 g (Ru) / m 2 . The last heat treatment is 30 minutes at 450 ° C.
La caractérisation électrochimique de l'élément est réalisée dans les mêmes conditions que celles décrites dans l'exemple 1. Le tableau (4) ci-dessous présente l'évolution du potentiel de la cathode et du gain en tension par comparaison avec une cathode en acier nu.
Plus de 25 cathodes activées ayant un revêtement 100% RuO2 ont été préparées dans des conditions voisines de celles décrites dans les exemples 3 et 4, sur des supports pleins en fer ou en acier ou sur des supports déployés en fer ou en acier, et caractérisées selon le mode opératoire décrit dans l'exemple 1. Le gain en tension moyen constaté par comparaison avec une cathode de même forme et de même nature mais non revêtue est de 200 ± 50 mV.More than 25 activated cathodes having a 100% RuO 2 coating were prepared under conditions similar to those described in Examples 3 and 4, on solid supports made of iron or steel or on supports deployed in iron or steel, and characterized by the procedure described in Example 1. The average voltage gain found by comparison with a cathode of the same shape and of the same nature but uncoated is 200 ± 50 mV.
On prépare une cathode activée de 72 cm2 pour un pilote de laboratoire d'électrolyse chlore-soude diaphragme. Le substrat est constitué d'un grillage en acier, utilisé sur les cellules industrielles. Le revêtement souhaité est de composition équimolaire en Ru et Ti, il est préparé selon le mode opératoire décrit dans l'exemple 2, il est déposé sur les deux faces du matériau support. La masse de revêtement est de 13,7 g/m2, soit 6,5 g(Ru)/m2, déposée en 4 couches. Aucune caractérisation électrochimique n'est faite sur cette cathode avant son montage sur la cellule pilote en raison de sa taille.A 72 cm 2 activated cathode is prepared for a chlorine-soda electrolysis laboratory pilot diaphragm. The substrate consists of a steel mesh, used on industrial cells. The desired coating is of equimolar composition in Ru and Ti, it is prepared according to the procedure described in Example 2, it is deposited on both sides of the support material. The coating weight is 13.7 g / m 2 , ie 6.5 g (Ru) / m 2 , deposited in 4 layers. No electrochemical characterization is made on this cathode before its mounting on the pilot cell because of its size.
La cathode activée est montée dans une cellule pilote d'électrolyse chlore-soude diaphragme utilisant un diaphragme Polyramix® et fonctionnant en continu 24h/24h, 7jours/7. Un jeu de soutirage et d'alimentation permet de maintenir constante la concentration des différents produits dans la cellule d'électrolyse. Les conditions de fonctionnement sont les suivantes : 2,5 kA/m2, 85°C, concentration soude dans la liqueur cathodique entre 120 g/l et 140 g/l, anode en titane déployé revêtu RuO2-TiO2. Une cathode en fer non revêtu issue du même support industriel est installée dans une cellule équivalente, fonctionnant avec les mêmes conditions opératoires. Le graphique (1) présente l'évolution du potentiel de ces deux cathodes sur 120 jours de fonctionnement.The activated cathode is mounted in a pilot cell electrolysis chlorine-soda diaphragm using a diaphragm Polyramix® and operating continuously 24h / 24h, 7days / 7. A racking and feeding game keeps the concentration of the different products in the electrolysis cell constant. The operating conditions are as follows: 2.5 kA / m 2 , 85 ° C., sodium hydroxide concentration in the cathode liquor between 120 g / l and 140 g / l, expanded titanium anode coated with RuO 2 -TiO 2 . An uncoated iron cathode from the same industrial support is installed in an equivalent cell, operating with the same operating conditions. Graph (1) shows the evolution of the potential of these two cathodes over 120 days of operation.
Dans ce graphique: ■ désigne cathode activée et ◆ désigne cathode acier nu.In this graph: ■ denotes activated cathode and ◆ denotes bare steel cathode.
Le gain en tension, obtenue par différence des deux potentiels, est de l'ordre de 180 mV sur la période 20 jours - 120 jours de fonctionnement.The gain in voltage, obtained by difference of the two potentials, is of the order of 180 mV over the
On prépare une cathode activée de 200 cm2 (5 cm x 40 cm) pour un pilote d'électrolyse chlorate de sodium. Un support en fer est revêtu sur ces deux faces d'un dépôt équimolaire en Ru et Ti selon le mode opératoire décrit dans l'exemple 2, hormis que le traitement thermique final est de 1 heure à 450°C. La masse de dépôt est de 10,3 g/m2, soit 4,9 g(Ru)/m2. Cette cathode est ensuite placée dans une cellule pilote d'électrolyse chlorate de sodium. L'anode est constituée d'un support en titane déployé revêtu RuO2-TiO2. Les conditions de fonctionnement de la cellule d'électrolyse chlorate de sodium sont les suivantes : [NaCl]= 200 g/l, [NaClO3] = 300 g/l, [Na2Cr2O7,2H2O]= 4 g/l, T= 80°C, distance anode-cathode = 3 mm, densité de courant = 4 kA/m2, fonctionnement en continu 24h/24 et 7jours/7. Un jeu de soutirage et d'alimentation permet de maintenir constante la concentration des différents produits dans la cellule d'électrolyse.A 200 cm 2 (5 cm × 40 cm) activated cathode is prepared for a sodium chlorate electrolysis pilot. An iron support is coated on these two faces with an equimolar deposit of Ru and Ti according to the procedure described in Example 2, except that the final heat treatment is 1 hour at 450 ° C. The deposit mass is 10.3 g / m 2 , 4.9 g (Ru) / m 2 . This cathode is then placed in a pilot cell of sodium chlorate electrolysis. The anode consists of an expanded titanium support coated RuO 2 -TiO 2 . The operating conditions of the sodium chlorate electrolysis cell are as follows: [NaCl] = 200 g / l, [NaClO 3 ] = 300 g / l, [Na 2 Cr 2 O 7 , 2H 2 O] = 4 g / l, T = 80 ° C, anode-cathode distance = 3 mm, current density = 4 kA / m 2 , continuous operation 24 hours a day, 7 days a week. A racking and feeding game keeps the concentration of the different products in the electrolysis cell constant.
En parallèle de cet essai, une cellule similaire fonctionne dans les mêmes conditions opératoires avec une cathode en fer non revêtu de même forme.In parallel with this test, a similar cell operates under the same operating conditions with an uncoated iron cathode of the same shape.
Ces deux cellules ont fonctionné pendant plus de 500 heures consécutives, une mesure de la tension de cellule est effectuée environ toutes les 50 heures. Sur toute la durée de l'essai, la tension de la cellule utilisant la cathode activée est inférieure de 200 ± 50 mV à la tension de la cellule utilisant une cathode en fer non revêtue.These two cells functioned for more than 500 consecutive hours, a measurement of the cell voltage is performed approximately every 50 hours. Throughout the duration of the test, the voltage of the cell using the activated cathode is 200 ± 50 mV lower than the voltage of the cell using an uncoated iron cathode.
Un substrat constitué d'une plaque de nickel pleine et un substrat constitué d'une plaque de fer pleine sont revêtues d'un dépôt équimolaire RuO2-TiO2 selon le mode opératoire décrit dans l'exemple 2 en répétant le cycle « enduction / séchage / calcination » jusqu'à obtenir un dépôt de 9 - 10 g/m2, soit 4,3 à 4,7 g(Ru)/m2. Le dernier traitement thermique est 30 minutes à 450°C. 3 couches sont nécessaires pour le support en fer, 6 couches pour le support en nickel : le dépôt est moins adhérent sur nickel que sur fer ; ces cathodes sont ensuite évaluées électrochimiquement selon le mode opératoire décrit dans l'exemple 1. Le graphique (2) présente les courbes de polarisation après stabilisation de chacune de ces cathodes. Nous constatons que la cathode revêtue à substrat nickel (courbe 1) présente de moins bonnes performances que la cathode revêtue à substrat fer (courbe 2) : pour une même densité de courant, le potentiel de la cathode activée support nickel est plus négatif que le potentiel de la cathode activée support fer.A substrate consisting of a solid nickel plate and a substrate consisting of a solid iron plate are coated with an equimolar RuO 2 -TiO 2 deposit according to the procedure described in Example 2 by repeating the "coating" cycle. drying / calcination "until a deposit of 9 - 10 g / m 2 , ie 4.3 to 4.7 g (Ru) / m 2 is obtained. The last heat treatment is 30 minutes at 450 ° C. 3 layers are necessary for the iron support, 6 layers for the nickel support: the deposit is less adherent on nickel than on iron; these cathodes are then evaluated electrochemically according to the procedure described in Example 1. Graph (2) shows the polarization curves after stabilization of each of these cathodes. We find that the nickel substrate coated cathode (curve 1) has poorer performance than the iron substrate coated cathode (curve 2): for the same current density, the potential of the nickel-supported activated cathode is more negative than the potential of the cathode activated iron support.
Une solution d'enduction équimolaire Ru / Ti est préparée par dissolution de 5,18 g de RuCl3,1,5H2O et de 3,1 ml de TiOCl2,2HCl (124,5 g (Ti)/l) dans 10 ml d'éthanol absolu. La solution est agitée pour permettre la dissolution des produits.An equimolar coating solution Ru / Ti is prepared by dissolving 5.18 g of RuCl 3 , 1.5H 2 O and 3.1 ml of TiOCl 2 , 2HCl (124.5 g (Ti) / l) in 10 ml of absolute ethanol. The solution is stirred to allow the products to dissolve.
Un premier support est constitué d'une plaque pleine en fer (3,5 x 2,5 cm) sur laquelle est soudée une tige en acier; la surface totale est de 33 cm2. Le support est préalablement sablé avec du Corindon puis rincé avec de l'acétone.A first support consists of a solid iron plate (3.5 x 2.5 cm) on which is welded a steel rod; the total surface is 33 cm 2 . The substrate is sandblasted with Corundum and then rinsed with acetone.
Un second support est constitué d'une plaque pleine en nickel (3,5 x 2,5 cm) sur laquelle est soudée une tige en nickel ; la surface totale est de 33 cm2. Le support est préalablement sablé avec du Corindon puis rincé avec de l'acétone.A second support consists of a solid nickel plate (3.5 x 2.5 cm) on which is welded a nickel rod; the total surface is 33 cm 2 . The substrate is sandblasted with Corundum and then rinsed with acetone.
Chaque support est ensuite enduit dans sa totalité avec la solution, placé dans une étuve à 120°C pendant 15 minutes, puis dans un four à 450°C pendant 15 minutes. Le dernier traitement thermique est 30 minutes à 450°C.Each support is then completely coated with the solution, placed in an oven at 120 ° C for 15 minutes, and then in an oven at 450 ° C for 15 minutes. The last heat treatment is 30 minutes at 450 ° C.
Le tableau (5) suivant présente l'évolution de la masse du dépôt en fonction du nombre de cycles « enduction / séchage / calcination » pour chacun des deux supports.
La caractérisation électrochimique des électrodes est réalisée dans les mêmes conditions que celles décrites dans l'exemple 1. Les tableaux (6) et (7) ci-après, présentent l'évolution du potentiel de la cathode support fer et du gain de tension par comparaison avec une cathode en fer nu- tableau (6) - et du potentiel de la cathode support nickel et du gain de tension par comparaison avec une cathode en fer nu - tableau 7 -.
A fort dégagement gazeux, le dépôt de la cathode à support fer se décroche, et les performances obtenues ensuite sont celles d'une cathode en fer non revêtue. La couleur du dépôt après le traitement thermique final indique la présence importante d'oxyde de fer.
Aucune détérioration de la cathode à support nickel n'est constatée après les différentes étapes de caractérisation électrochimique, et le gain en tension par comparaison avec une cathode en fer nu est amélioré par la caractérisation électrochimique.No deterioration of the nickel-supported cathode is observed after the various stages of electrochemical characterization, and the voltage gain compared with a bare iron cathode is improved by the electrochemical characterization.
Claims (19)
- Process for the formation of a coating of metal oxides comprising at least one precious metal from Group VIII of the Periodic Table of the elements, optionally in combination with titanium and/or zirconium, on an electrically conductive substrate, the said process consisting in applying, to the said substrate, a solution comprising at least one organometallic compound and in then converting the said organometallic compound(s) to metal oxide (s) by means of a heat treatment, the said process being characterized in that the electrically conductive substrate is made of steel or of iron and in that the only solution applied to the said substrate is a non-aqueous solution of metal acetylacetonate or of a mixture of metal acetylacetonates dissolved in a (plurality of) solvent(s) which specifically dissolve(s) each metal acetylacetonate, the solvent(s) being chosen from alcohols, ketones, chloromethanes or a mixture of two or more solvents mentioned above.
- Process according to Claim 1, characterized in that the precious metal from Group VIII of the Periodic Table of the elements is ruthenium, rhodium, palladium, osmium, iridium or platinum.
- Process according to Claim 2, characterized in that the precious metal is ruthenium or iridium.
- Process according to Claim 3, characterized in that the precious metal is ruthenium.
- Process according to Claim 1, characterized in that the alcohol is ethanol or isopropanol.
- Process according to Claim 1, characterized in that the ketone is acetone.
- Process according to Claim 1, characterized in that the chloromethane is chloroform.
- Process according to any one of Claims 1 to 7, characterized in that the metal acetylacetonate solution is obtained by dissolution of the said metal acetylacetonate in its specific solvent or in a mixture of solvents comprising the specific solvent.
- Process according to any one of Claims 1 to 7, characterized in that the solution comprising several metal acetylacetonates is obtained:- either by dissolution of the said metal acetylacetonates in a mixture of solvents comprising the specific solvents for the said metal acetylacetonates;- or by mixing solutions comprising only a single metal acetylacetonate which are obtained by dissolution of the said metal acetylacetonate in a specific solvent or in a mixture of solvents comprising the specific solvent for the said acetylacetonate.
- Process according to any one of Claims 1 to 9, characterized in that, in order to obtain the coating of metal oxide(s), the substrate made of steel or of iron is pretreated, in a first stage, and then, in a second stage, the solution comprising the metal acetylacetonate(s) is deposited on the said pretreated substrate and the substrate thus coated is dried and then calcined.
- Process according to Claim 10, characterized in that the drying is carried out at a temperature at most equal to 150°C.
- Process according to Claim 10, characterized in that the substrate coated by the metal acetylacetonate(s) is calcined under air or else under an inert gas enriched with oxygen, at a temperature at least equal to 300°C and preferably at a temperature of between 400°C and 600°C, for a period of time ranging from 10 minutes to 2 hours.
- Process according to Claim 10, characterized in that the second stage is repeated at least once and is preferably repeated between 2 and 6 times.
- Electrically conductive substrate made of steel or of iron carrying a coating of metal oxides which is formed by means of a process according to one of Claims 1 to 13.
- Use of the electrically conductive substrate according to Claim 14 in the production of an activated cathode.
- Use of an activated cathode according to Claim 15, in the electrolysis of aqueous solutions of alkali metal chlorides.
- Use according to Claim 16, characterized in that the aqueous solutions of alkali metal chlorides are aqueous sodium chloride solutions.
- Process for the manufacture of chlorine and alkali metal hydroxide by electrolysis of the corresponding chloride by means of a cathode according to Claim 15.
- Process for the manufacture of alkali metal chlorates by electrolysis of the corresponding chloride by means of a cathode according to Claim 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL04742353T PL1608795T3 (en) | 2003-03-28 | 2004-03-25 | Method for the formation of a coating of metal oxides on an electrically-conducting substrate, resultant activated cathode and use thereof for the electrolysis of aqueous solutions of alkaline metal chlorides |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0303867A FR2852973B1 (en) | 2003-03-28 | 2003-03-28 | PROCESS FOR FORMING A COATING OF METAL OXIDES ON AN ELECTROCONDUCTIVE SUBSTRATE; RESULTING ACTIVE CATHODE AND USE THEREOF FOR THE ELECTROLYSIS OF ACQUEUS SOLUTIONS OF ALKALINE COIL CHORIDES. |
| FR0303867 | 2003-03-28 | ||
| PCT/FR2004/000746 WO2004087992A2 (en) | 2003-03-28 | 2004-03-25 | Method for the formation of a coating of metal oxides on an electrically-conducting substrate, resultant activated cathode and use thereof for the electrolysis of aqueous solutions of alkaline metal chlorides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1608795A2 EP1608795A2 (en) | 2005-12-28 |
| EP1608795B1 true EP1608795B1 (en) | 2006-06-14 |
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| EP04742353A Expired - Lifetime EP1608795B1 (en) | 2003-03-28 | 2004-03-25 | Method for the formation of a coating of metal oxides on an electrically-conducting substrate, resultant activated cathode and use thereof for the electrolysis of aqueous solutions of alkaline metal chlorides |
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| Country | Link |
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| US (1) | US7790233B2 (en) |
| EP (1) | EP1608795B1 (en) |
| JP (1) | JP4532471B2 (en) |
| KR (1) | KR101111369B1 (en) |
| CN (1) | CN1795291B (en) |
| AT (1) | ATE330043T1 (en) |
| BR (1) | BRPI0408905A (en) |
| CA (1) | CA2520584C (en) |
| DE (1) | DE602004001230T2 (en) |
| ES (1) | ES2270380T3 (en) |
| FR (1) | FR2852973B1 (en) |
| MX (1) | MXPA05010353A (en) |
| PL (1) | PL1608795T3 (en) |
| UA (1) | UA80610C2 (en) |
| WO (1) | WO2004087992A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006283143A (en) * | 2005-03-31 | 2006-10-19 | Dainippon Printing Co Ltd | Method for producing metal oxide film |
| GB0714021D0 (en) * | 2007-07-18 | 2007-08-29 | Green Metals Ltd | Improvements in anode materials |
| US8124556B2 (en) * | 2008-05-24 | 2012-02-28 | Freeport-Mcmoran Corporation | Electrochemically active composition, methods of making, and uses thereof |
| SG174447A1 (en) * | 2009-05-26 | 2011-10-28 | Agency Science Tech & Res | Muteins of the pyrroline-5-carboxylate reductase 1 |
| CN102505127A (en) * | 2011-12-29 | 2012-06-20 | 文广 | Preparation method for noble metal modified titanium anode materials |
| WO2015137193A1 (en) * | 2014-03-12 | 2015-09-17 | Jsr株式会社 | Semiconductor device production composition and pattern formation method using said semiconductor device production composition |
| CN106521433A (en) * | 2015-09-09 | 2017-03-22 | 宁波江丰电子材料股份有限公司 | Ring part structure and machining method thereof |
| IT201900020026A1 (en) * | 2019-10-30 | 2021-04-30 | Industrie De Nora Spa | ELECTRODE FOR THE ELECTROLYTIC EVOLUTION OF HYDROGEN |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3850668A (en) | 1972-06-05 | 1974-11-26 | Johnson Matthey Co Ltd | Impregnation of graphite with ruthenium compounds |
| US4300992A (en) | 1975-05-12 | 1981-11-17 | Hodogaya Chemical Co., Ltd. | Activated cathode |
| US4100049A (en) * | 1977-07-11 | 1978-07-11 | Diamond Shamrock Corporation | Coated cathode for electrolysis cells |
| FR2583781A1 (en) * | 1985-06-24 | 1986-12-26 | Atochem | CATHODE FOR ELECTROLYSIS AND METHOD FOR MANUFACTURING THE SAME CATHODE |
| FR2596776B1 (en) * | 1986-04-03 | 1988-06-03 | Atochem | CATHODE FOR ELECTROLYSIS AND A METHOD FOR MANUFACTURING SAID CATHODE |
| JPH0766816B2 (en) * | 1989-01-13 | 1995-07-19 | 東洋インキ製造株式会社 | Method for manufacturing gas diffusion type composite electrode |
| KR100479485B1 (en) * | 1995-08-04 | 2005-09-07 | 마이크로코팅 테크놀로지, 인크. | Chemical Deposition and Powder Formation Using Thermal Spraying of Near Supercritical and Supercritical Fluids |
| US5864051A (en) * | 1997-11-10 | 1999-01-26 | Uop | Selective oxidation catalyst process for preparing the catalyst and process using the catalyst |
| JP3383838B2 (en) * | 1999-02-25 | 2003-03-10 | 独立行政法人産業技術総合研究所 | Method for producing metal oxide and method for forming fine pattern |
| FR2797646B1 (en) * | 1999-08-20 | 2002-07-05 | Atofina | CATHODE FOR USE IN THE ELECTROLYSIS OF AQUEOUS SOLUTIONS |
| US7258899B1 (en) * | 2001-12-13 | 2007-08-21 | Amt Holdings, Inc. | Process for preparing metal coatings from liquid solutions utilizing cold plasma |
| US20040077494A1 (en) * | 2002-10-22 | 2004-04-22 | Labarge William J. | Method for depositing particles onto a catalytic support |
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- 2004-03-25 PL PL04742353T patent/PL1608795T3/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2270380T3 (en) | 2007-04-01 |
| US20060263614A1 (en) | 2006-11-23 |
| US7790233B2 (en) | 2010-09-07 |
| FR2852973B1 (en) | 2006-05-26 |
| BRPI0408905A (en) | 2006-03-28 |
| PL1608795T3 (en) | 2006-11-30 |
| MXPA05010353A (en) | 2005-12-14 |
| JP4532471B2 (en) | 2010-08-25 |
| WO2004087992A2 (en) | 2004-10-14 |
| CA2520584C (en) | 2011-08-23 |
| KR20050114265A (en) | 2005-12-05 |
| KR101111369B1 (en) | 2012-04-09 |
| CN1795291B (en) | 2011-08-31 |
| JP2006521469A (en) | 2006-09-21 |
| ATE330043T1 (en) | 2006-07-15 |
| FR2852973A1 (en) | 2004-10-01 |
| ZA200507825B (en) | 2007-01-31 |
| EP1608795A2 (en) | 2005-12-28 |
| DE602004001230D1 (en) | 2006-07-27 |
| DE602004001230T2 (en) | 2007-04-19 |
| CA2520584A1 (en) | 2004-10-14 |
| UA80610C2 (en) | 2007-10-10 |
| CN1795291A (en) | 2006-06-28 |
| WO2004087992A3 (en) | 2005-02-17 |
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