WO1979000840A1 - Electrodes for electrolytic processes,especially metal electrowinning - Google Patents
Electrodes for electrolytic processes,especially metal electrowinning Download PDFInfo
- Publication number
- WO1979000840A1 WO1979000840A1 PCT/EP1979/000020 EP7900020W WO7900840A1 WO 1979000840 A1 WO1979000840 A1 WO 1979000840A1 EP 7900020 W EP7900020 W EP 7900020W WO 7900840 A1 WO7900840 A1 WO 7900840A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- coating
- dioxide
- weight
- platinum
- Prior art date
Links
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000005363 electrowinning Methods 0.000 title description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000013535 sea water Substances 0.000 claims abstract description 4
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 claims abstract 2
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 platinum group metal Chemical class 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- ABUBSBSOTTXVPV-UHFFFAOYSA-H [U+6].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [U+6].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ABUBSBSOTTXVPV-UHFFFAOYSA-H 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 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
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- 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
Definitions
- the invention relates to electrodes for electrolytic processes, in particular to electrodes having an active surface containing manganese dioxide, and to electrolytic processes using such electrodes, especially as anodes for metal electrowinning.
- Anodes made of manganese oxides have been known for a long time and are disclosed, for instance, in U.S. Patent Specifications 1,296,188 and 1,143,828. Such anodes have been used in the electrowinning of metals such as zinc, copper and nickel. For various reasons, such as the difficulties met with in forming them, such anodes are not suitable for commercial use, however.
- Another proposed electrode is described in U.S. Patent Specification 3,855,084, wherein titanium particles are cemented together with thermally-deposited manganese dioxide and a second or outer coating of electrodeposited manganese dioxide is provided thereon.
- US Patent Specification 3,616,302 describes an electrowinning anode, comprising a sandblasted titanium substrate coated with a thin intermediate layer of platimun, palladium or rhodium or their alloys, on which a relatively thick layer of manganese dioxide is electroplated.
- U.S. Patent Specification 4,028,215 currently an electrode which comprises a valve metal substrates, an intermediate semi-conductive layer of tin and antimony oxides and a top coating of manganese dioxide.
- U.S. Patent Specification 4,077,586 proposed an electrode having a corrosion resistant substrate coated with ß-manganese dioxide, chemideposited by thermal decomposition of an alcoholic solution of manganese nitrate, and activated by ß-ray Irradiation or by the addition of up to 5% by weight of at least one metal from groups IB, IIB, IVA, VA, VB, VIB, VIIB and VIII of the Periodic Table, excluding the platinum group metals, gold and silver.
- the corrosion resistant Substrate was optionally provided with a thin porous intermediate coating, such as a valve metal or a platinum group metal or oxide thereof, and the activated manganese dioxide optionally contained up to 20% by weight of Silicon dioxide, ß-lead dioxide or tin dioxide as stabilizer.
- a thin porous intermediate coating such as a valve metal or a platinum group metal or oxide thereof
- the activated manganese dioxide optionally contained up to 20% by weight of Silicon dioxide, ß-lead dioxide or tin dioxide as stabilizer.
- An object of the invention is to provide an improved electrode, having a coating of manganese dioxide which selectively favors oxygen evolution, the electrode being particularly useful for electrowinning metals fr ⁇ m dilute Solutions.
- an electrode for electrolytic processes comprises an electrically-conductive corrosion-resistant substrate having an electrocatalytic coating, characterized in that the coating contains a mixture of at least one platinum group metal and manganese dioxide dispersed in one another throughout the coating, in a ratio of from 8: 2 to 3: 7 by weight, of the platinum group metal (s) to the manganese metal of the manganese dioxide.
- the coating contains platinum in a ratio of from 7: 3 to 4: 6 by weight.
- the platinum-group metal / manganese dioxide coating preferably also contains, as a stabilizer, titanium oxide, silicon dioxide, ß-lead dioxide and / or tin dioxide, most preferably tin dioxide.
- a stabilizer is especially useful when the manganese content exceeds the platinum group metal content, in order to prevent corrosion of the coating during electrolysis.
- the coating may include a filier, e.g. particles or fibers of an inert material such as silica or alumina, particles of titanium or, possible, zirconium silicate.
- the mixed coating of platinum group metal (s) and manganese dioxide may also contain, as dopant, up to about 5% by weight as metal of the manganese dioxide, at least one additional metal selected from groups IB, IIB, IVA, VA, VB, VIB and VIIB of the periodic table and iron, cobalt and nickel.
- tin dioxide the preferred amount is about 5% to 10% by weight of tin to the total weight of the platinum group metal (s) plus the manganese metal of the manganese dioxide.
- the platinum group metals are ruthenium, rhodium, palladium, osmium, iridium and platinum. Platinum metal is preferred and is mentioned hereafter by way of example. However, it is to be understood that alloys such as platinum-rhodium and platinum-palladium can also be used. Also, in some instances, it may be advantageous to alloy the platinum group metal (s) with one or more non-platinum group metals, for example an alloy or an intermetallic compound with one of the valve metals, ie titanium, zirconium, hafnium , vanadium, niobium and tantalum, or with another transition metal, for example a metal such as tungsten, manganese or cobalt.
- the substrate may consist of any of the aforementioned valve metals or alloys thereof, porous sintered titanium being preferred.
- porous sintered titanium being preferred.
- other electrically-conductive and corrosion-resistant substrates may be used, such as expanded graphite.
- the platinum group metal (s) and manganese dioxide with possible additional components may be co-deposited chemically from solutions of appropriate salts which are painted, sprayed or otherwise applied on the substrate and then subjected to heat treatment, this process being repeated until a sufficiently thick layer has been built up.
- thin layers of different components eg alternate platinum layers and layers of mixed ß-manganese dioxide and tin dioxide
- the components are effectively mixed and dispersed in one another throughout the coating, possibly with diffusion between the layers, in contrast to the cited prior art coatings in which the manganese dioxide was applied as a separate top layer.
- the manganese dioxide is preferably in the ß form, being chemi-deposited by thermal decomposition of a solution of manganese nitrate.
- the platinum-group metal / manganese dioxide layer may be applied directly to the Substrate or to an intermediate layer, e.g. of co-deposited tin and antimony oxides or tin and bismuth oxides or to intermediate layers consisting of one or more platinum group metals or their oxides, mixtures or mixed crystals of platinum group metals and valve metal oxides, intermetallics of platinum group metals and non- platinum group metals, and so forth.
- an intermediate layer e.g. of co-deposited tin and antimony oxides or tin and bismuth oxides
- intermediate layers consisting of one or more platinum group metals or their oxides, mixtures or mixed crystals of platinum group metals and valve metal oxides, intermetallics of platinum group metals and non- platinum group metals, and so forth.
- the coating comprises 30 to 80 parts by weight of platinum, 20 to 70 parts by weight (as Mn metal) of ß-manganese dioxide and 2 to 10 parts by weight (as Sn metal) of tin dioxide.
- This embodiment of an electrode of the invention when used as anode for metalwinning from dilute solutions, has been found to have selective properties favoring oxygen evolution and the deposition of certain metal oxides, eg the anodic deposition of UO 2 from seawater.
- the platinum metal plays three roles: as an electronic conductor; as oxygen evolution catalyst (the wanted reaction); and as chlorine evolution poison (the un wanted reaction). Not only is ß-manganese dioxide isomorphous with UO 2 , but also it acts as a catalyst for UO 2 deposition.
- the tin dioxide in addition to stabilizing the ß-manganese dioxide, acts as a source of active oxygen (H 2 O 2 ).
- Another aspect of the invention is a method of electro-recovering metals, especially Strategy metals such as uranium, yttrium and ytterbium, or their oxides, eg from dilute saline waters such as seawater, which comprises using as anode an electrode aecording to the invention, as defined above. This method is preferably carried out with deposition of the metal oxide in oxygen developing conditions.
- Fig. 1 is a graph showing faraday efficiency of UO 2 deposition as ordinate plotted against the ß-Mn0 2 content by weight of Mn to the total weight of Mn + Pt group metal ⁇ as abscissa, obtained by use of the electrode described in detail in Example I below;
- Fig. 2 is a graph showing anode potential as ordinate plotted against current density as abscissa, obtained using the electrodes described in detail in Example III below BEST MODES FOR CARRYING OUT THE INVENTION
- Expanded graphite anode bases were coated as in Example I, except that the coating solution additionally contained tin nitrate.
- the finished coatings contained ß-MnO 2 (50% by weight as Mn metal), Pt (40% -50% by weight as metal) and SnO 2 (0% -10% by weight as Sn metal). These anodes were used, under the same conditions as Example I, for UO 2 recovery. An Optimal faraday efficiency for UO 2 deposition was achieved with an Sn content of from about 3% to 6%. No corrosion or dissolution of the MnO 2 was observed.
- Fig. 2 is a potentiostatic curve of such a sintered titanium anode coated with a chemi-deposited coating containing 45% by weight Pt, 50% by weight ß-MnO 2 (as Mn metal) and 5% by weight SnO 2 (as Sn metal).
- the corresponding curve for a platinum-coated sintered titanium anode is shown as a dashed line.
- Reaction (ii) is favored by the presence of SnO 2 , which acts as a source of active oxygen by complexing H 2 O 2 in addition to stabilizing the MnO 2 phase.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB12054/78 | 1978-03-28 | ||
| GB1205478 | 1978-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1979000840A1 true WO1979000840A1 (en) | 1979-10-18 |
Family
ID=9997596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1979/000020 WO1979000840A1 (en) | 1978-03-28 | 1979-03-27 | Electrodes for electrolytic processes,especially metal electrowinning |
Country Status (7)
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56116892A (en) * | 1980-02-20 | 1981-09-12 | Japan Carlit Co Ltd:The | Insoluble anode for generating oxygen and preparation thereof |
| US4289591A (en) * | 1980-05-02 | 1981-09-15 | General Electric Company | Oxygen evolution with improved Mn stabilized catalyst |
| DE3132726A1 (de) * | 1981-08-19 | 1983-03-03 | Basf Ag, 6700 Ludwigshafen | Verfarhen zur herstellung von alkylsubstituierten benzaldehyden |
| US6517964B2 (en) * | 2000-11-30 | 2003-02-11 | Graftech Inc. | Catalyst support material for fuel cell |
| US20060047270A1 (en) * | 2004-08-27 | 2006-03-02 | Shelton Brian M | Drug delivery apparatus and method for automatically reducing drug dosage |
| JP4961825B2 (ja) * | 2006-05-09 | 2012-06-27 | アタカ大機株式会社 | 電気化学反応用陽極 |
| JP4793086B2 (ja) * | 2006-05-09 | 2011-10-12 | アタカ大機株式会社 | 酸素発生用電極 |
| JP4972991B2 (ja) * | 2006-05-09 | 2012-07-11 | アタカ大機株式会社 | 酸素発生用電極 |
| JP4695206B2 (ja) * | 2009-06-18 | 2011-06-08 | 国立大学法人北陸先端科学技術大学院大学 | 金属回収方法および金属回収装置 |
| KR20130112037A (ko) | 2010-09-24 | 2013-10-11 | 데트 노르스키 베리타스 에이에스 | 이산화탄소의 전기화학적 환원을 위한 방법 및 장치 |
| CN114561642B (zh) * | 2022-02-27 | 2025-05-02 | 湖南株冶有色金属有限公司 | 一种锰氧化物复合涂层电极的制备方法及其应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2652152A1 (de) * | 1975-11-18 | 1977-09-15 | Diamond Shamrock Techn | Elektrode fuer elektrolytische reaktionen und verfahren zu deren herstellung |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1143828A (en) * | 1913-05-17 | 1915-06-22 | Percy Claude Cameron Isherwood | Process for manufacturing anodes. |
| US1296188A (en) * | 1918-07-24 | 1919-03-04 | Siemens Ag | Process for making anodes of solid manganese peroxid. |
| GB1195871A (en) * | 1967-02-10 | 1970-06-24 | Chemnor Ag | Improvements in or relating to the Manufacture of Electrodes. |
| US3616302A (en) * | 1967-02-27 | 1971-10-26 | Furerkawa Electric Co Ltd The | Insoluble anode for electrolysis and a method for its production |
| GB1206863A (en) * | 1968-04-02 | 1970-09-30 | Ici Ltd | Electrodes for electrochemical process |
| US3647641A (en) * | 1970-10-26 | 1972-03-07 | Gen Electric | Reactant sensor and method of using same |
| IT959730B (it) * | 1972-05-18 | 1973-11-10 | Oronzio De Nura Impianti Elett | Anodo per sviluppo di ossigeno |
| US3855084A (en) * | 1973-07-18 | 1974-12-17 | N Feige | Method of producing a coated anode |
| IT1050048B (it) * | 1975-12-10 | 1981-03-10 | Oronzio De Nora Impianti | Elettrodi rivestiti con biossido di manganese |
| US4028215A (en) * | 1975-12-29 | 1977-06-07 | Diamond Shamrock Corporation | Manganese dioxide electrode |
-
1979
- 1979-03-27 EP EP79100915A patent/EP0004386B1/en not_active Expired
- 1979-03-27 JP JP54500619A patent/JPH0355555B2/ja not_active Expired - Lifetime
- 1979-03-27 CA CA324,270A patent/CA1129811A/en not_active Expired
- 1979-03-27 WO PCT/EP1979/000020 patent/WO1979000840A1/de unknown
- 1979-03-27 DE DE7979100915T patent/DE2964080D1/de not_active Expired
- 1979-03-28 ZA ZA791474A patent/ZA791474B/xx unknown
- 1979-10-26 EP EP79900366A patent/EP0015943A1/en not_active Withdrawn
- 1979-11-26 US US06/097,345 patent/US4285799A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2652152A1 (de) * | 1975-11-18 | 1977-09-15 | Diamond Shamrock Techn | Elektrode fuer elektrolytische reaktionen und verfahren zu deren herstellung |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0015943A1 (en) | 1980-10-01 |
| EP0004386A3 (en) | 1979-10-31 |
| JPS55500178A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1980-03-27 |
| ZA791474B (en) | 1980-04-30 |
| CA1129811A (en) | 1982-08-17 |
| EP0004386B1 (en) | 1982-11-24 |
| EP0004386A2 (en) | 1979-10-03 |
| DE2964080D1 (en) | 1982-12-30 |
| JPH0355555B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1991-08-23 |
| US4285799A (en) | 1981-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3212327B2 (ja) | 電解用電極 | |
| TWI247052B (en) | Electrocatalytic coating with lower platinum group metals and electrode made therefrom | |
| US4072586A (en) | Manganese dioxide electrodes | |
| US7247229B2 (en) | Coatings for the inhibition of undesirable oxidation in an electrochemical cell | |
| US6527939B1 (en) | Method of producing copper foil with an anode having multiple coating layers | |
| KR101022978B1 (ko) | 가스 발생용 전극 및 이의 제조방법 | |
| US4484999A (en) | Electrolytic electrodes having high durability | |
| JPH0713310B2 (ja) | 電気化学プロセスにおいて、特にアルカリ金属塩化物の電解用の電解槽において使用される陰極、及びその製造法 | |
| US4285799A (en) | Electrodes for electrolytic processes, especially metal electrowinning | |
| JPS622038B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | ||
| EP0715002A1 (en) | Stable coating solutions for preparing electrocatalytic mixed oxide coatings on metal substrates or metal-coated conductive substrates, and dimensionally stable anodes produced from such solutions | |
| JPH0465913B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | ||
| JP2000110000A (ja) | 電解プロセスにおける酸素発生用アノ―ド | |
| US4233340A (en) | Process for preparing insoluble electrode | |
| JPH11302892A (ja) | 電解用電極およびその製造方法 | |
| EP0027051A1 (en) | Coated metal electrode with improved barrier layer and methods of manufacture and use thereof | |
| JPH08176876A (ja) | 電気化学プロセス用電極及び該電極の使用方法 | |
| JP2020193371A (ja) | オゾン生成用電極 | |
| JPH0774470B2 (ja) | 酸素発生用陽極の製法 | |
| JP3724096B2 (ja) | 酸素発生用電極とその製造方法 | |
| US4212725A (en) | Electrodes for electrolysis purposes | |
| JP2836890B2 (ja) | 有機物電解用電極及びその製造方法 | |
| US3677917A (en) | Electrode coatings | |
| US4010091A (en) | Novel electrode for electrolysis cell | |
| JP3658823B2 (ja) | 電解用電極およびその製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Designated state(s): BR DK JP SU US |
|
| AL | Designated countries for regional patents |
Designated state(s): CH DE FR GB SE |