CN103476970A - Anode for electrowinning and electrowinning method using same - Google Patents
Anode for electrowinning and electrowinning method using same Download PDFInfo
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- CN103476970A CN103476970A CN2012800161229A CN201280016122A CN103476970A CN 103476970 A CN103476970 A CN 103476970A CN 2012800161229 A CN2012800161229 A CN 2012800161229A CN 201280016122 A CN201280016122 A CN 201280016122A CN 103476970 A CN103476970 A CN 103476970A
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- electrowinning
- anode
- oxide
- catalyst layer
- amorphous
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- 238000005363 electrowinning Methods 0.000 title claims abstract description 279
- 238000000034 method Methods 0.000 title description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 109
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 82
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 77
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 72
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 61
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000010936 titanium Substances 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 33
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- 229910052715 tantalum Inorganic materials 0.000 claims description 22
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052741 iridium Inorganic materials 0.000 claims description 13
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 2
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 2
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 2
- 229910001362 Ta alloys Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 229910001080 W alloy Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 41
- 239000001301 oxygen Substances 0.000 abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 abstract description 41
- 229910052719 titanium Inorganic materials 0.000 abstract description 31
- 229910000978 Pb alloy Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 118
- 230000000052 comparative effect Effects 0.000 description 55
- 230000000694 effects Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000001149 thermolysis Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000007086 side reaction Methods 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 239000002243 precursor Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 12
- 238000005979 thermal decomposition reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- -1 platinum metals Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910003174 MnOOH Inorganic materials 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JODOMBGKVAIYRQ-UHFFFAOYSA-N [Nb].[Ta].[Ti] Chemical compound [Nb].[Ta].[Ti] JODOMBGKVAIYRQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
Abstract
Provided is an anode for electrowinning such that, in electrowinning using a sulfuric acid-based electrolyte solution, the electric potential for oxygen generation is lower than for a lead electrode, lead alloy electrode, and coated titanium electrode, the electrolysis voltage for electrowinning can be reduced, and the basic units for electric energy can be reduced for a desired metal. This anode can be used as the anode for electrowinning of various types of metal and has superior mass productability. The anode for electrowinning is used in the electrowinning that uses a sulfuric acid-based electrolyte solution, and a catalyst layer that includes noncrystalline ruthenium oxide and noncrystalline tantalum oxide is formed on a conductive base substance.
Description
Technical field
Anode and the electroextraction that uses this anode for the electrowinning that the electrowinning of the metal that the present invention relates to expect by electrowinning is used, being particularly related to and using sulfuric acid is electrolytic solution, and anodic reaction produces anode and the electroextraction that uses this anode for electrowinning that the electrowinning of oxygen uses.
Background technology
The electrowinning of metal, by by the energising after the aqueous solution of the ion that contains the metal that wish extracts (below, be called electrolytic solution) of anode and cathode dipping, separates out this metal and carries out on negative electrode.Example as representational electrowinning, can enumerate following method: the use process will contain copper, zinc, nickel, cobalt, lead, platinum metals (platinum, iridium, ruthenium, palladium etc.), precious metal (silver, gold), other transition metal, rare earth metal or be generically and collectively referred to as any above ore grindings such as metallic element of essential metal, use suitable acid etc. that metal ion is dissolved, then extract the electrolytic solution of the preparations such as process of metal target ion, by the electrowinning metal.In addition, electrowinning also comprises: in order to be recovered in the mobile equipments such as primary cell, secondary cell, fuel cell, mobile phone and other electronics, electrical and electronic parts, plated steel sheet, plating ornaments etc. the metal or alloy for various uses, metal or alloy after using is pulverized, the process of process dissolved metal ions etc., the electrolytic solution that use contains the metal target ion, by electrolytic regeneration and extract metal.In addition, electrowinning also comprises: through from the process of plating pulp thickening metal ion etc., use the electrolytic solution that contains the metal target ion, by the electrowinning metal.Composition beyond the metal ion of the electrolytic solution that electrowinning uses if be conceived to, have that to take sulfuric acid that sulfuric acid is main electrolyte ingredient be electrolytic solution or the chlorination system electrolytic solution that hydrochloric acid or muriate be main electrolyte ingredient of take, in addition, use and take pH regulator as the various electrolytic solution of the acid or alkaline aqueous solution as basis.
The energy of electrowinning consumption is the product of the electric weight of electrolysis voltage and energising, and the amount of metal that the negative electrode place obtains and this electric weight are proportional.Therefore, electrolysis voltage is lower, the power consumption of the needed electrowinning of metal of the extraction of unit weight (below, be designated as the unit power consumption amount) less.This electrolysis voltage is the potential difference of anode and negative electrode, the metal difference that negative electrode obtains, and cathodic reaction is also different, its reactive species difference, the current potential of negative electrode is also different.On the other hand, if anodic reaction with the kind illustration of above-mentioned electrolytic solution, sulfuric acid is that electrolytic solution produces oxygen, chlorination system electrolytic solution produces chlorine.For example, in the electrowinning carried out in commercialization at present, it is electrolytic solution that the electrowinning of the metals such as copper, zinc, nickel, cobalt is used sulfuric acid.In the situation that use this sulfuric acid, be electrolytic solution, the current potential of the anode while producing oxygen changes along with the material of anode use.For example, in the material that low material and catalytic activity are high in the generation catalytic activity for oxygen, the high material of catalytic activity, the current potential of anode is lower.Therefore, in the situation that use identical electrolytic solution to carry out electrowinning, in order to reduce the unit power consumption amount, anode is used the high material of catalytic activity, and the current potential that reduces anode is important and necessary.
In addition, using sulfuric acid is that the anode of electrowinning of electrolytic solution is except the catalytic activity height of the generation to oxygen, for contingent reaction on the anode beyond the generation of oxygen (below, be designated as side reaction), contrary with the generation to oxygen, require catalytic activity low.For example, in the electrowinning of zinc or copper or cobalt or nickel etc., except the zine ion or cupric ion or cobalt ion or nickel ion of the essential component as in electrolytic solution, also may comprise other metal ion.As such metal ion, be well known that mn ion, lead ion etc.If use the electrolytic solution that contains mn ion or lead ion to carry out electrowinning, hydroxyl oxidize manganese (MnOOH) and/or Manganse Dioxide (MnO are separated out in the oxidation of generation+divalent mn ion on anode on anode
2) etc. manganic compound, plumbic oxide (PbO is separated out in or the oxidation of generation+divalent lead ion on anode
2).These reactions occur with the generation of oxygen that as sulfuric acid is the anodic reaction of electrolytic solution on anode simultaneously, manganic compound and plumbic oxide are low to the catalytic activity of the generation of oxygen, and electroconductibility is not high yet, therefore, hinder the generation reaction of the oxygen on anode, consequently, become the current potential that makes anode and rise, the reason that electrolysis voltage increases.In addition, for example, at the additive component using cobalt ion as electrolytic solution, but not add in the situation of electrolytic solution as the metal ion of electrowinning object, the generation of oxygen occurs on anode, simultaneously as side reaction, the oxidation of generation+divalent cobalt ion, the hydroxy cobalt oxide (CoOOH) generated is thus separated out on anode, and the separating out equally on anode with above-mentioned manganic compound and plumbic oxide, become the reason that electrolysis voltage is increased.The metal oxide that side reaction on anode as above causes and/or metal hydroxy oxide compound separate out and accumulation causes that electrolysis voltage rises, become the reason that the life-span weather resistance that makes anode reduces simultaneously.
Due to above-mentioned reason, using sulfuric acid is that the anode of the electrowinning of electrolytic solution is preferably used the material that meets following condition: 1) high to the catalytic activity of the generation of oxygen; 2) even to the side reaction of precipitating metal oxide compound on anode and/or metal hydroxy oxide compound with do not contain metal ingredient, precipitate also on anode, adhere to or the catalytic activity of the side reaction built up low; 3) therefore, there is the highly selective to the generation of oxygen; 4) consequently, the current potential of anode is low, and in other words, the superpotential of antianode reaction is little, even and proceed electrowinning, the anode potential that does not also exist the impact by side reaction to cause rises; 5) therefore, electrolysis voltage is low, even and proceed electrowinning and also can keep low electrolysis voltage, thus, little for the unit power consumption quantitative change of electrowinning metal target; Life-span and the weather resistance of the anode that 6) simultaneously, does not exist the impact by side reaction to cause reduce; 7) generation of oxygen had to high-durability.
On the other hand, using sulfuric acid is the electrowinning anode of electrolytic solution, as representational material except using lead electrode and lead alloy, can also use on the titanium matrix electrode as catalyst layer coating platinum metals or platinum group metal oxide or their mixture and/or composite oxides (below, be designated as coating titanium electrode) etc.Concrete example as such coating titanium electrode, it is the titanium electrode with the catalyst layer coating containing iridium oxide, particularly can use with the mixed oxide that contains iridium oxide and tantalum oxide in catalyst layer, or the coating titanium electrode of the catalyst layer coating that in this mixed oxide, other metal of remix or metal oxide form.In addition, if enumerate, coating titanium electrode is extended to the example that utilizes field beyond electrowinning, disclose the coating titanium electrode that the anode of the various electrolysis process of the use aqueous solution such as plating, the manufacture of electrolytic metal paper tinsel, salt electrolysis, brine electrolysis manufacture, electrolytic functional water manufacture is used in patent documentation 1～patent documentation 7.In addition, in patent documentation 1～patent documentation 7, disclosed anode also comprises the generation that not only can be used for oxygen, but also can be used for the anode of the generation of chlorine.In addition, precursor solution of using while using thermal decomposition method to make electrowinning with coating titanium electrode and preparation method thereof is disclosed in patent documentation 8.On the other hand, the inventor discloses the electrowinning that comprises coating titanium electrode with anode and has used the electroextraction of this anode in patent documentation 9 and patent documentation 10.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 6-101083 communique
Patent documentation 2: Japanese kokai publication hei 9-87896 communique
Patent documentation 3: TOHKEMY 2007-246987 communique
Patent documentation 4: TOHKEMY 2008-50675 communique
Patent documentation 5: TOHKEMY 2010-507017 communique
Patent documentation 6: TOHKEMY 2011-17084 communique
Patent documentation 7: TOHKEMY 2011-503359 communique
Patent documentation 8: No. 2009/0288958 specification sheets of U.S. Patent Application Publication
Patent documentation 9: No. 4516617 communique of Japanese Patent
Patent documentation 10: No. 4516618 communique of Japanese Patent
Summary of the invention
Invent problem to be solved
As mentioned above, the inventor is in patent documentation 9, disclose and be formed with containing the electrowinning of the zinc of the catalyst layer of amorphous iridium oxide with anode on conductive base and use the electroextraction of the zinc of this anode, thus, with the electrowinning of zinc in the past, with anode and electroextraction, compare, known: anode potential and electrolysis voltage to the generation of oxygen during electrowinning zinc may reduce, and can suppress separating out of hydroxyl oxidize manganese that the side reaction as anode occurs and/or Manganse Dioxide etc.At this, can suppress to be as the hydroxyl oxidize manganese of side reaction and/or the reason of separating out of Manganse Dioxide, the catalyst layer that contains amorphous iridium oxide is high to the catalytic activity of the generation of oxygen, therefore, the generation of oxygen is carried out than side reaction is preferential, therefore, the generation that electric current during energising is used as the oxygen of main reaction consumes, but not by side-reaction consumes.That is, as long as the anode that use sulfuric acid is the electrowinning of electrolytic solution can improve the catalytic activity to the generation of oxygen, the generation of oxygen is preferentially occurred than other side reaction, can suppress thus side reaction.On the other hand, disclose in patent documentation 10 and be formed with containing the electrowinning of the cobalt of the catalyst layer of amorphous ruthenium oxide with anode on conductive base and use the electroextraction of the cobalt of this anode, thus, with the electrowinning of the cobalt in the past that uses chlorination system electrolytic solution, with anode and electroextraction, compare, known: anode potential and electrolysis voltage to the generation of chlorine may reduce, and can suppress separating out of hydroxy cobalt oxide that the side reaction as anode occurs etc.In these prior aries, about using sulfuric acid, be the zinc of electrolytic solution or the electrowinning of cobalt, found optionally there is high catalytic activity containing the generation of the oxygen of the catalyst layer antianode of amorphous iridium oxide, on the other hand, about the electrowinning of the cobalt that uses chlorination system electrolytic solution, found optionally there is high catalytic activity containing the generation of the chlorine of the catalyst layer antianode of amorphous ruthenium oxide.
But, about using sulfuric acid, be the electrowinning of electrolytic solution, seek further to reduce anode potential by the catalytic activity of further raising antianode reaction, and further reduce electrolysis voltage thus.In addition, using sulfuric acid, be the electrowinning of the metal of electrolytic solution,, in electrowinning using the generation of oxygen as anodic reaction, seek for other metal, for example, the electrowinning of the metals such as copper, nickel also can further reduce anode and the electroextraction of electrolysis voltage.In addition, seek to reduce the unit power consumption amount in the electrowinning that use sulfuric acid is electrolytic solution, seek to be formed with anode or the lower anode of manufacturing cost of more cheap catalyst layer simultaneously, but not use the anode of the expensive metal such containing iridium as the catalyst layer of composition.In addition, about using sulfuric acid, be the electroextraction of electrolytic solution, also seek electrolysis voltage and can further reduce, and can reduce the cost of anode, further reduce the electroextraction of the cost of electrowinning.
Therefore, the present invention is in order to respond the invention of above-mentioned requirements, its purpose is, a kind of electroextraction is provided, using sulfuric acid, be in the electrowinning of electrolytic solution, with lead electrode, lead alloy, coating titanium electrode is compared, the current potential of the generation of oxygen is low, thus, can reduce the electrolysis voltage of electrowinning, the unit power consumption amount of minimizing to the metal of expectation, and the anode that can be used as the electrowinning of various metals is used, simultaneously, with using sulfuric acid, be that coating titanium electrode used in the electrowinning of electrolytic solution is compared, can reduce the cost of catalyst layer, can provide production good electrowinning anode, and be in the electroextraction of electrolytic solution using sulfuric acid, current potential and the electrolysis voltage of anode are low, therefore, can reduce the unit power consumption amount of electrowinning, and the initial cost of anode and maintenance cost are also low, therefore, can reduce the cost of whole electrowinning technique.
For solving the means of problem
The inventor has carried out various research in order to solve above-mentioned problem, found that: by being formed with electrowinning containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide with anode on conductive base and using the electroextraction of this anode can solve above-mentioned problem, completed thus the present invention.
That is,, in order to solve above-mentioned existing problem, electrowinning of the present invention is with anode and use the electroextraction of this anode to have following formation.
The described electrowinning anode of a first aspect of the present invention is to be the electrowinning anode of the electrowinning of electrolytic solution for using sulfuric acid, has the formation be formed with on conductive base containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide.
By this formation, there is following effect:
(1) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide to being that the generation of the oxygen of electrolytic solution optionally demonstrates high catalytic activity from sulfuric acid, make the anode potential of the generation of oxygen is significantly reduced.
(2) compare with being formed with containing the electrode of the catalyst layer of crystalline state iridium oxide on conductive base or being formed with on conductive base containing the electrode of the catalyst layer of amorphous iridium oxide, sulfuric acid is that the current potential of generation of oxygen of electrolytic solution is low, can suppress side reaction simultaneously, catalytic activity to the generation of oxygen is high, using sulfuric acid, be in the electrowinning of electrolytic solution, with the situation of using other anode, compare, no matter the kind of the metal extracted at the negative electrode place how, can reduce electrolysis voltage.
(3) be formed with the anode containing the catalyst layer of amorphous iridium oxide with use, particularly be formed with the anode containing the catalyst layer of amorphous iridium oxide and amorphous tantalum oxide, by sulfuric acid, be that the situation that electrolytic solution carries out electrowinning is compared, can further reduce the current potential of anode, can reduce electrolysis voltage, creative high, and novel, unique.
(4) low with the current potential of anode to the electrowinning of the generation of oxygen, the generation of oxygen is preferentially carried out than other side reaction, thereby suppressed hydroxyl oxidize manganese, Manganse Dioxide, plumbic oxide, hydroxy cobalt oxide etc., at electrowinning, with the anode place, separates out and build up such side reaction.
(5) price of ruthenium is only below 1/3 of iridium, therefore, can realize being greater than the catalyst layer that contains amorphous iridium oxide and the amorphous tantalum oxide high catalytic activity to the catalytic activity of the generation of oxygen by the more cheap catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide.
At this, as conductive base, preferably the valve metal such as titanium, tantalum, zirconium, niobium, tungsten, molybdenum or titanium-tantalum, titanium-niobium, titanium-palladium, titanium-tantalum-niobium etc. (for example be take the alloy of alloy, valve metal and platinum metals that valve metal is main body and/or transition metal or conductive diamond, the diamond of doped with boron), still be not limited to these.In addition, its shape can be the different shapes such as three-dimensional porous body that tabular, netted, bar-shaped, sheet, tubulose, wire, porous is tabular, vesicular, just spherical metallics are combined into.As conductive base, except above-mentioned substance, the material that can also use the metal that the quilts such as described valve metal, alloy, conductive diamond overlayed on beyond the valve metals such as iron, nickel or electroconductibility ceramic surface to form.
In addition, in the scope of the electrolysis voltage that catalyst layer also can be in the time reducing electrowinning, contain other composition except amorphous ruthenium oxide and amorphous tantalum oxide.
As other such composition, can enumerate: platinum, iridium, ruthenium, tungsten, tantalum, iridium oxide, titanium oxide, niobium oxides etc., but be not limited to these.
The described electrowinning anode of a second aspect of the present invention is to be the electrowinning anode of the electrowinning of electrolytic solution for using sulfuric acid, there is following formation: be formed with the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on conductive base, with the anode that is formed with the catalyst layer formed with amorphous tantalum oxide by amorphous iridium oxide on conductive base, compare, more than electrolysis voltage in the time of can making electrowinning reduces 0.02V, perhaps, with the anode that is formed with the catalyst layer formed with amorphous tantalum oxide by the crystalline state ruthenium oxide on conductive base, compare, more than electrolysis voltage in the time of can making electrowinning reduces 0.05V.
According to this formation, there is following effect:
(1) impact of not oxidated iridium grade in an imperial examination three compositions (other composition), can improve the catalytic activity to the generation of oxygen reliably, no matter the kind of the metal extracted at the negative electrode place how, can both obtain the reducing effect of electrolysis voltage.
The described electrowinning anode of a third aspect of the present invention is to be the electrowinning anode of the electrowinning of electrolytic solution for using sulfuric acid, has and be formed with forming of the catalyst layer that is comprised of amorphous ruthenium oxide and amorphous tantalum oxide on conductive base.
According to this formation, there is following effect:
(1), by the mixture that makes electrowinning be amorphous ruthenium oxide and amorphous tantalum oxide with the catalyst layer of anode, thereby can access, to can be applicable to use sulfuric acid be the weather resistance in the electrowinning of electrolytic solution.
At this, in patent documentation 6, one of as a comparative example, it is extremely low as the weather resistance of coating layer in sulphuric acid soln of metal ingredient that ruthenium and tantalum that the thermolysis of usining by 480 ℃ obtains are disclosed, but, such result is the problem produced at the crystalline state ruthenium oxide that contains thermolysis and obtain in the situation that carry out at the temperature more than at least 350 ℃, on the other hand, the inventor finds: will be formed with ruthenium oxide in the mixture with amorphous tantalum oxide for the electrowinning of the catalyst layer of non-crystalline state state with anode as being the electrowinning anode of the electrowinning of electrolytic solution for using sulfuric acid, the problem of the weather resistance of the such generation to oxygen of patent documentation 6 can not occur.Particularly, electrowinning of the present invention with anode sulfuric acid be in electrolytic solution with the common electrolytic condition in the electrowinning that is produced as anodic reaction of oxygen, the current density of unit electrode area is 0.1A/cm
2below under such electrolytic condition, bring into play good weather resistance.
Below, further describe content of the present invention.For form the method containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide on conductive base, except after will being coated on conductive base containing the precursor solution of ruthenium and tantalum, beyond the thermal decomposition method of heat-treating, can also use the various physical vapor depositions such as sputtering method or CVD method or chemical vapor deposition method etc. under specified temperature.In addition, making electrowinning of the present invention with in the method for anode, especially further narration utilizes the making method of thermal decomposition method.For example, the ruthenium of the various forms such as inorganic-containing compound, organic compound, ion, complex compound and the precursor solution of tantalum are coated on the titanium matrix, it,, when at least lower than the temperature range of 350 ℃, carrying out thermolysis, is formed to the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on the titanium matrix.For example, to be dissolved with the butanol solution of ruthenium chloride hydrate and tantalum chloride as precursor solution, it is coated on the titanium matrix while carrying out thermolysis, for example, if the mol ratio of the ruthenium in butanol solution and tantalum is 30:70, when heat decomposition temperature is made as to 280 ℃, form the catalyst layer of the mixture that comprises amorphous ruthenium oxide and amorphous tantalum oxide.In addition, after being coated with described precursor solution, even carry out thermolysis under 260 ℃, form similarly the catalyst layer of the mixture that comprises amorphous ruthenium oxide and amorphous tantalum oxide.
By thermal decomposition method in the situation that form the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on conductive base, whether the kind of this metal ingredient and mol ratio in contained all metal ingredients etc. is different at precursor solution in the situation that contains the metal ingredient except ruthenium and tantalum in mol ratio, heat decomposition temperature and precursor solution according to ruthenium contained in the precursor solution be coated with on the titanium matrix and tantalum, contain amorphous ruthenium oxide in catalyst layer and amorphous tantalum oxide also can change.For example, metal ingredient composition in addition contained in precursor solution is identical, and as metal ingredient, only contain in the situation of ruthenium and tantalum, demonstrate in precursor solution the mol ratio of ruthenium less, obtain the larger trend of scope containing the heat decomposition temperature of the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide.In addition, the condition that forms the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide not only is subject to the impact of the mol ratio of such metal ingredient, also along with preparation method and the material of precursor solution, the kind of the ruthenium for example, used while preparing precursor solution and the starting material of tantalum, solvent species, the additive that adds in order to promote thermolysis and the difference of concentration and change.
Therefore, at electrowinning of the present invention, use in anode, condition while by thermal decomposition method, forming the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is not limited to the mol ratio of use, ruthenium and tantalum of butanols solvent in above-mentioned thermal decomposition method and the scope of heat decomposition temperature related to this, above-mentioned condition is an example wherein only, and electrowinning of the present invention comprises all methods that can on conductive base, form the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide except method shown in above-mentioned by the making method of anode.For example, such method also comprises the disclosed method that heat tracing is processed in the preparation process of precursor solution in patent documentation 8 certainly.In addition, about the formation of the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide, can be according to by X-ray diffraction method commonly used, do not observe the diffraction peak corresponding with ruthenium oxide and do not observe the diffraction peak corresponding with tantalum oxide and learn.
The described invention of fourth aspect is first aspect to the described electrowinning anode of any one in the third aspect, and it has the formation that in described catalyst layer, the mol ratio of ruthenium and tantalum is 30:70.
Form according to this, except first aspect, to the effect obtained in any one in the third aspect, also there is following effect:
(1) at precursor solution, the composition beyond contained metal ingredient is identical, and only contain in the situation of ruthenium and tantalum as metal ingredient, can see in precursor solution the mol ratio of ruthenium less, obtain the larger trend of scope containing the heat decomposition temperature of the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide, production is good.
The 5th described invention in aspect is first aspect to the described electrowinning anode of any one in fourth aspect, and it has the formation that is formed with middle layer between catalyst layer and conductive base.
Form according to this, except the effect that first aspect to any one in fourth aspect obtains, also there is following effect:
(1) form middle layer between catalyst layer and conductive base, the surface of the conductive base of coating simultaneously, thus, even electrolyte permeability is in catalyst layer, also can prevent that electrolytic solution from arriving conductive base, therefore, conductive base can be by the acidic electrolysis corrosion, and the electric current that can suppress to be caused by corrosion product becomes between conductive base and catalyst layer can not smooth and easy mobile phenomenon.
(2) in the situation that be formed with and comprise the oxide compound different with the catalyst layer of anode from electrowinning of the present invention or the middle layer of composite oxides; with the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide, compare; catalytic activity to the generation of oxygen is low; therefore; even in the situation that electrolyte permeability is to catalyst layer; in middle layer, the generation of oxygen can be than preferentially occurring in catalyst layer, so weather resistance can be protected conductive base thus than catalyst height.Simultaneously, higher oxide compound or the composite oxides coating conductive base by the weather resistance with such, compare the corrosion of the conductive base that can suppress to be caused by electrolytic solution with the situation that there is no middle layer.
At this, middle layer is lower than catalyst layer to the catalytic activity of the generation of oxygen, but abundant coating conductive base, effect with the corrosion that suppresses conductive base, can be formed by complex chemical compounds such as the metallic compounds such as the carbonaceous materials such as metal, alloy, boron-doped diamond, oxide compound or sulfide, composite oxide of metal etc.For example, in the situation that formed by metal, the film of preferred tantalum, niobium etc., in addition, in the situation that formed preferred tantalum, niobium, tungsten, molybdenum, titanium, platinum etc. by alloy.In addition, use the middle layer of the carbonaceous materials such as boron-doped diamond also to there is same effect.The middle layer consisted of above-mentioned metal, alloy, carbonaceous material can be passed through the whole bag of tricks such as the various physical vapor depositions such as thermal decomposition method, sputtering method or CVD method or chemical vapor deposition method, hot dipping method, electrochemical plating and form.As the middle layer consisted of the metallic compound such as oxide compound or sulfide or composite oxide of metal, preference is as, middle layer consisted of the oxide compound containing the crystalline state iridium oxide etc.Particularly in the situation that make catalyst layer by thermal decomposition method, the manufacturing process that the middle layer consisted of oxide compound or composite oxides by identical thermal decomposition method formation is conducive to simplify electrowinning use anode.
The 6th described invention in aspect is the 5th described electrowinning anode in aspect, and it has a kind of the forming of forming of described middle layer in the alloy of tantalum, niobium, tungsten, molybdenum, titanium, platinum or the arbitrary metal in them.
Form according to this, except the effect that the 5th aspect obtains, also there is following effect:
(1) can pass through the whole bag of tricks such as the various physical vapor depositions such as thermal decomposition method, sputtering method or CVD method or chemical vapor deposition method, hot dipping method, electrochemical plating and form middle layer, production is good.
The 7th described invention in aspect is the 5th described electrowinning anode in aspect, has the formation of described middle layer containing crystalline state iridium oxide and amorphous tantalum oxide.
Form according to this, except the effect that the 5th aspect obtains, also there is following effect:
(1) ruthenium oxide in catalyst layer and the iridium oxide in middle layer belong to same crystallographic system, and interatomic distance approaches, therefore and the adaptation between the catalyst layer formed on middle layer good, weather resistance significantly improves.
At this, contain the middle layer of crystalline state iridium oxide and amorphous tantalum oxide except after will being coated on conductive base containing the precursor solution of iridium and tantalum, under specified temperature beyond heat treated thermal decomposition method, can also make by methods such as the various physical vapor depositions such as sputtering method or CVD method or chemical vapor deposition methods.For example, in the situation that thermal decomposition method, the middle layer that the crystalline state iridium oxide preferably obtained by making precursor solution containing iridium and tantalum carry out thermolysis at the temperature of 400 ℃～550 ℃ and amorphous tantalum oxide form etc.
The described invention of eight aspect is the described electrowinning of any one anode in first aspect to the seven aspects, any formation that the metal with electrowinning is copper, zinc, nickel, cobalt, platinum, gold and silver, indium, lead, ruthenium, rhodium, palladium, iridium.
Form according to this, the effect that any one obtains in first aspect to the seven aspects, also there is following effect:
(1) current potential due to the generation of oxygen is low, therefore, can reduce the electrolysis voltage of electrowinning, reduces the unit power consumption amount to metal, can use as the anode of the electrowinning of various metals, and versatility is good.
The described electroextraction of a ninth aspect of the present invention is that use sulfuric acid is the electroextraction of electrolytic solution, has the formation of using the metal that in first aspect to the eight aspect, for the described electrowinning of any one, the anode extraction is expected.
According to this formation, there is following effect:
(1) using sulfuric acid, be in the electroextraction of electrolytic solution, electrowinning is low with current potential and the electrolysis voltage of anode, can reduce the unit power consumption amount of electrowinning, and electrowinning is also low by initial cost and the maintenance cost of anode, can reduces the cost of whole electrowinning technique.
The tenth described invention in aspect is the 9th described electroextraction in aspect, any formation that the metal with electrowinning is copper, zinc, nickel, cobalt, platinum, gold and silver, indium, lead, ruthenium, rhodium, palladium, iridium.
It has following effect:
(1) electrolysis voltage is low, also can keep low electrolysis voltage even proceed electrowinning, unit power consumption quantitative change for the electrowinning metal target is little, the electrowinning that does not exist the impact by side reaction to cause reduces by life-span and the weather resistance of anode, can be for a long time and electrowinning metal target stably, the efficiency of electrowinning, have good stability.
The invention effect
According to the present invention, be achieved as follows effect.
1) using sulfuric acid, be in the electrowinning of metal of electrolytic solution, compared with the past, can reduce the current potential of electrowinning with the generation of the oxygen of anode, therefore, no matter the kind of the metal extracted is how, the electrolysis voltage in the time of all can reducing electrowinning, thus, can significantly reduce the unit power consumption amount.
2) in addition, compared with the past, can reduce the current potential of electrowinning with the generation of the oxygen of anode, therefore, can suppress in the various side reactions that occur on anode for electrowinning, can in long-term electrowinning, to suppress the rising of electrolysis voltage.
3) when thering is above-mentioned effect, not or alleviated and remove due to the necessity of side reaction at the oxide compound of separating out accumulation on anode, oxyhydroxide, other compound for electrowinning, therefore, the electrowinning that has suppressed to be caused by this operation infringement of anode, therefore, extended the life-span of electrowinning with anode.
4) when thering is above-mentioned effect, do not need or reduced and removed due to the operation of side reaction at the oxide compound of separating out on anode or building up, oxyhydroxide, other compound for electrowinning, therefore, suppress or alleviated electrowinning in the electrowinning and change with the maintenance of anode.In addition, suppressed due to such necessity that electrowinning is ended in operation of removing, therefore, can be continuously and more stably carry out electrowinning.
5) when thering is above-mentioned effect, suppressed the precipitate on anode for electrowinning, therefore, do not exist because this precipitate has limited the situation of electrowinning by the effective surface area of anode, maybe can prevent that but electrowinning is inhomogeneous with the electrolysis area of anode, can prevent that metal is inhomogeneous on negative electrode separates out or generates the poor metal of smoothness, suppresses the quality that metal is difficult to the metal that reclaims or extract and reduces.
6) in addition, for above-mentioned reasons, due to the situation that does not have metal inhomogeneous growth on negative electrode, therefore, can prevent that the metal of growing on negative electrode from arriving electrowinning and being short-circuited with anode, prevent from carrying out again electrowinning.In addition, suppress metal inhomogeneous growth and dendritic growth on negative electrode, therefore, can shorten the interelectrode distance of electrowinning with anode and negative electrode, can suppress the increase of the electrolysis voltage that the resistance losses of electrolytic solution causes.
7) in addition, as mentioned above, eliminated the variety of issue that the electrowinning that produces due to side reaction causes with the precipitate on anode, thereby can stablize and carry out continuously electrowinning, can reduce maintenance and management operations in electrowinning, the management of product of the metal easily extracted simultaneously.In addition, can reduce the cost of the electrowinning of long-term electrowinning with anode.
8), according to the present invention, with the coating titanium electrode that is formed with the catalyst layer that contains iridium oxide in the past, compare in addition,, by using ruthenium oxide, reduced the cost of catalyst layer, in addition, because heat decomposition temperature is low, therefore also reduced the cost of the formation operation of catalyst layer.
9) when thering is above-mentioned effect, using sulfuric acid, be in the electrowinning of various metals of electrolytic solution, can significantly reduce the manufacturing cost of whole electrowinning.
The accompanying drawing explanation
Fig. 1 is the figure of the X-ray diffraction image that utilizes the electrowinning of embodiment 1, embodiment 2, comparative example 1 to obtain with anode.
Embodiment
Below, utilize embodiment, comparative example to describe the present invention in detail, the present invention is not limited to following examples, and for example, the present invention also can be applicable to the electrowinning of other metal beyond zinc, copper, cobalt.
［ electrowinning of zinc ］
Embodiment 1
After by commercially available titanium plate (long 5cm, wide 1cm, thick 1mm), in 10% oxalic acid solution, under 90 ℃, dipping carries out etch processes in 60 minutes, washed, drying.Then, to the butanols (n-C containing the concentrated hydrochloric acid of 6vol%
4h
9oH) add ruthenium trichloride trihydrate (RuCl in solution
33H
2o) and tantalum pentachloride (TaCl
5), the mol ratio that makes ruthenium and tantalum is 30:70, according to metal, converts, the summation of ruthenium and tantalum is 50g/L, thereby makes coating fluid.This coating fluid is coated on above-mentioned dried titanium plate, under 120 ℃ dry 10 minutes, then thermolysis 20 minutes in being held in the electric furnace of 260 ℃.This coating, drying, thermolysis are repeated 5 times altogether, on the titanium plate as conductive base, form catalyst layer, thereby make the electrowinning anode of embodiment 1.
By X-ray diffraction method, the electrowinning of embodiment 1 is carried out to structure elucidation with anode, consequently: as shown in Figure 1, do not see and RuO in the X-ray diffraction image
2suitable diffraction peak, also do not see and Ta
2o
5suitable diffraction peak.In addition, although can see the diffraction peak of Ti, this is produced by the titanium plate.That is,, in the electrowinning of embodiment 1 is used anode, formed the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on the titanium plate.
Preparation is by the ZnSO of 0.80mol/L
4the electrolytic solution formed with the sulfuric acid of 2.0mol/L, using zine plate (2cm * 2cm) as cathode dipping in this electrolytic solution.In addition, the electrowinning of above-described embodiment 1 is embedded in tetrafluoroethylene support processed with anode, at the electrode area that will contact with electrolytic solution, is limited in 1cm
2state under, the same interelectrode distance subtend configuration that separates regulation in electrolytic solution with above-mentioned negative electrode.Then, between electrowinning is with anode and negative electrode circulation take electrowinning with the electrode area of anode as reference current density be 10mA/cm
2or 50mA/cm
2in arbitrary Faradaic current, carry out the electrowinning of zinc, measure the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.In addition, electrolytic solution is 40 ℃.
Embodiment 2
With anode, the heat decomposition temperature except will form catalyst layer the time becomes 280 ℃ from 260 ℃ the electrowinning of embodiment 2, by the method identical with embodiment 1, is made.By X-ray diffraction method, the electrowinning of embodiment 2 is carried out to structure elucidation with anode, consequently: as shown in Figure 1, do not see and RuO
2suitable diffraction peak, also do not see and Ta
2o
5suitable diffraction peak.In addition, although can see the diffraction peak of Ti, this is produced by the titanium plate.That is,, in the electrowinning of embodiment 2 is used anode, formed the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on the titanium plate.
Preparation is by the ZnSO of 0.80mol/L
4the electrolytic solution formed with the sulfuric acid of 2.0mol/L, using zine plate (2cm * 2cm) as cathode dipping in this electrolytic solution.In addition, the electrowinning of above-described embodiment 2 is embedded in tetrafluoroethylene support processed with anode, at the electrode area that will contact with electrolytic solution, is limited in 1cm
2state under, the same interelectrode distance subtend configuration that separates regulation in electrolytic solution with above-mentioned negative electrode.Then, between electrowinning is with anode and negative electrode circulation take electrowinning with the electrode area of anode as reference current density be 10mA/cm
2or 50mA/cm
2in arbitrary Faradaic current, carry out the electrowinning of zinc, measure the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.In addition, electrolytic solution is 40 ℃.
(comparative example 1)
With anode, the heat decomposition temperature except will form catalyst layer the time becomes 360 ℃ from 260 ℃ the electrowinning of comparative example 1, by the method identical with embodiment 1, is made.By X-ray diffraction method, the electrowinning of comparative example 1 is carried out to structure elucidation with anode, consequently: as shown in Figure 1, seen and RuO
2suitable diffraction peak, but do not see and Ta
2o
5suitable diffraction peak.In addition, although can see the diffraction peak of Ti, this is produced by the titanium plate.That is, the electrowinning of comparative example 1 with anodic formation containing the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide.
Preparation is by the ZnSO of 0.80mol/L
4the electrolytic solution formed with the sulfuric acid of 2.0mol/L, using zine plate (2cm * 2cm) as cathode dipping in this electrolytic solution.In addition, the electrowinning of above-mentioned comparative example 1 is embedded in tetrafluoroethylene support processed with anode, at the electrode area that will contact with electrolytic solution, is limited in 1cm
2state under, the same interelectrode distance subtend configuration that separates regulation in electrolytic solution with above-mentioned negative electrode.Then, between electrowinning is with anode and negative electrode circulation take electrowinning with the electrode area of anode as reference current density be 10mA/cm
2or 50mA/cm
2in arbitrary Faradaic current, carry out the electrowinning of zinc, measure the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.In addition, electrolytic solution is 40 ℃.
(comparative example 2)
After by commercially available titanium plate (long 5cm, wide 1cm, thick 1mm), in 10% oxalic acid solution, under 90 ℃, dipping carries out etch processes in 60 minutes, washed, drying.Then, to the butanols (n-C containing the concentrated hydrochloric acid of 6vol%
4h
9oH) add chloro-iridic acid hexahydrate (H in solution
2irCl
66H
2o) and tantalum chloride (TaCl
5), the mol ratio that makes iridium and tantalum is 80:20, according to metal, converts, the summation of iridium and tantalum is 70g/L, thereby makes coating fluid.This coating fluid is coated on above-mentioned dried titanium plate, under 120 ℃ dry 10 minutes, then thermolysis 20 minutes in being held in the electric furnace of 360 ℃.This coating, drying, thermolysis are repeated 5 times altogether, on the titanium plate as conductive base, form catalyst layer, thereby make the electrowinning anode of comparative example 2.
By X-ray diffraction method, the electrowinning of comparative example 2 is carried out to structure elucidation with anode, consequently: do not see and IrO in the X-ray diffraction image
2suitable diffraction peak, also do not see and Ta
2o
5suitable diffraction peak.That is,, in the electrowinning of comparative example 2 is used anode, formed the catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide on the titanium plate.
Preparation is by the ZnSO of 0.80mol/L
4the electrolytic solution formed with the sulfuric acid of 2.0mol/L, using zine plate (2cm * 2cm) as cathode dipping in this electrolytic solution.In addition, the electrowinning of above-mentioned comparative example 2 is embedded in tetrafluoroethylene support processed with anode, at the electrode area that will contact with electrolytic solution, is limited in 1cm
2state under, the same interelectrode distance subtend configuration that separates regulation in electrolytic solution with above-mentioned negative electrode.Then, between electrowinning is with anode and negative electrode circulation take electrowinning with the electrode area of anode as reference current density be 10mA/cm
2or 50mA/cm
2in arbitrary Faradaic current, carry out the electrowinning of zinc, measure the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.In addition, electrolytic solution is 40 ℃.
The voltage between terminals when electrowinning of use above-described embodiment 1, embodiment 2, comparative example 1, comparative example 2 carries out electrowinning with anode is as shown in table 1～table 4.
[table 1]
[table 2]
[table 3]
[table 4]
As shown in table 1, in the electrowinning of zinc, in the situation that use the anode for electrowinning that has formed the embodiment 1 of the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide by the thermolysis of 260 ℃, with respect to using thermolysis by 360 ℃ to form the situation with anode containing the electrowinning of the comparative example 1 of the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide, electrolysis voltage has reduced 0.17V～0.19V.In addition, as shown in table 2, in the situation that use anode electrowinning for of embodiment 1, formed the situation containing the electrowinning use anode of the comparative example 2 of the catalyst layer of amorphous iridium oxide and amorphous tantalum oxide with respect to use, electrolysis voltage has reduced 0.05V～0.06V.That is, in the situation that use has formed the anode for electrowinning (embodiment 1) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide, with use
The situation that has formed the anode for electrowinning (comparative example 1) of the catalyst layer that contains crystalline state ruthenium oxide and amorphous tantalum oxide is compared, electrolysis voltage significantly reduces, in addition, the situation that has formed the anode for electrowinning (comparative example 2) of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with use is compared, and also can further reduce electrolysis voltage.
In addition, as shown in table 3, in the electrowinning of zinc, in the situation that use the anode for electrowinning that has formed the embodiment 2 of the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide by the thermolysis of 280 ℃, with respect to using thermolysis by 360 ℃ to form the situation with anode containing the electrowinning of the comparative example 1 of the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide, electrolysis voltage has reduced 0.15V～0.20V.In addition, as shown in table 4, in the situation that use anode electrowinning for of embodiment 2, formed the situation containing the electrowinning use anode of the comparative example 2 of the catalyst layer of amorphous iridium oxide and amorphous tantalum oxide with respect to use, electrolysis voltage has reduced 0.04V～0.06V.; in the situation that use has formed the anode for electrowinning (embodiment 2) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide; with the situation of the anode for electrowinning (comparative example 1) that has formed the catalyst layer that contains crystalline state ruthenium oxide and amorphous tantalum oxide, compare; electrolysis voltage significantly reduces; in addition; the situation that has formed the anode for electrowinning (comparative example 2) of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with use is compared, and also can further reduce electrolysis voltage.
［ electrowinning of copper ］
Embodiment 3
The electrolytic solution of embodiment 1 is become to the CuSO by 0.60mol/L
4with the electrolytic solution that the sulfuric acid of 0.90mol/L forms, other condition is identical with embodiment 1, carries out the electrowinning of copper, measures the voltage between terminals (electrolysis voltage) between electrowinning use anode-negative electrode simultaneously.
Embodiment 4
The electrolytic solution of embodiment 2 is become to the CuSO by 0.60mol/L
4with the electrolytic solution that the sulfuric acid of 0.90mol/L forms, other condition is identical with embodiment 2, carries out the electrowinning of copper, measures the voltage between terminals (electrolysis voltage) between electrowinning use anode-negative electrode simultaneously.
(comparative example 3)
The electrolytic solution of comparative example 1 is become to the CuSO by 0.60mol/L
4with the electrolytic solution that the sulfuric acid of 0.90mol/L forms, other condition is identical with comparative example 1, carries out the electrowinning of copper, measures the voltage between terminals (electrolysis voltage) between electrowinning use anode-negative electrode simultaneously.
(comparative example 4)
The electrolytic solution of comparative example 2 is become to the CuSO by 0.60mol/L
4with the electrolytic solution that the sulfuric acid of 0.90mol/L forms, other condition is identical with comparative example 2, carries out the electrowinning of copper, measures the voltage between terminals (electrolysis voltage) between electrowinning use anode-negative electrode simultaneously.
The voltage between terminals when electrowinning of use above-described embodiment 3, embodiment 4, comparative example 3, comparative example 4 carries out electrowinning with anode is as shown in table 5～table 8.
[table 5]
[table 6]
[table 7]
[table 8]
As shown in table 5, in the electrowinning of copper, in the situation that use the anode for electrowinning that has formed the embodiment 3 of the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide by the thermolysis of 260 ℃, with respect to using thermolysis by 360 ℃ to form the situation with anode containing the electrowinning of the comparative example 3 of the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide, electrolysis voltage has reduced 0.11V～0.16V.In addition, as shown in table 6, in the situation that use anode electrowinning for of embodiment 3, formed the situation containing the electrowinning use anode of the comparative example 4 of the catalyst layer of amorphous iridium oxide and amorphous tantalum oxide with respect to use, electrolysis voltage has reduced 0.05V～0.07V.; in the situation that use has formed the anode for electrowinning (embodiment 3) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide; the situation that has formed the anode for electrowinning (comparative example 3) of the catalyst layer that contains crystalline state ruthenium oxide and amorphous tantalum oxide with use is compared; electrolysis voltage significantly reduces; in addition; the situation that has formed the anode for electrowinning (comparative example 4) of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with use is compared, and also can further reduce electrolysis voltage.
In addition, as shown in table 7, in the electrowinning of copper, in the situation that use the anode for electrowinning that has formed the embodiment 4 of the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide by the thermolysis of 280 ℃, with respect to using thermolysis by 360 ℃ to form the situation with anode containing the electrowinning of the comparative example 3 of the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide, electrolysis voltage has reduced 0.10V～0.16V.In addition, as shown in table 8, in the situation that use anode electrowinning for of embodiment 4, formed the situation containing the electrowinning use anode of the comparative example 4 of the catalyst layer of amorphous iridium oxide and amorphous tantalum oxide with respect to use, electrolysis voltage has reduced 0.04V～0.07V.; in the situation that use has formed the anode for electrowinning (embodiment 4) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide; with the situation of the anode for electrowinning (comparative example 3) that has formed the catalyst layer that contains crystalline state ruthenium oxide and amorphous tantalum oxide, compare; electrolysis voltage significantly reduces; in addition; the situation that has formed the anode for electrowinning (comparative example 4) of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with use is compared, and also can further reduce electrolysis voltage.
［ electrowinning of cobalt ］
Embodiment 5
Except the electrolytic solution by embodiment 1 becomes the CoSO by 0.30mol/L
4with 2.0 * 10
-3the electrolytic solution that the sulfuric acid of mol/L forms, be made as 10mA/cm by current density
2in addition, other condition is identical with embodiment 1, carries out the electrowinning of cobalt, measures the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.
Embodiment 6
Except the electrolytic solution by embodiment 2 becomes the CoSO by 0.30mol/L
4with 2.0 * 10
-3the electrolytic solution that the sulfuric acid of mol/L forms, be made as 10mA/cm by current density
2in addition, other condition is identical with embodiment 2, carries out the electrowinning of cobalt, measures the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.
(comparative example 5)
Except the electrolytic solution by comparative example 1 becomes the CoSO by 0.30mol/L
4with 2.0 * 10
-3the electrolytic solution that the sulfuric acid of mol/L forms, be made as 10mA/cm by current density
2in addition, other condition is identical with comparative example 1, carries out the electrowinning of cobalt, measures the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.
(comparative example 6)
Except the electrolytic solution by comparative example 2 becomes the CoSO by 0.30mol/L
4with 2.0 * 10
-3the electrolytic solution that the sulfuric acid of mol/L forms, be made as 10mA/cm by current density
2in addition, other condition is identical with comparative example 2, carries out the electrowinning of cobalt, measures the voltage between terminals (electrolysis voltage) between anode-negative electrode for electrowinning simultaneously.
The voltage between terminals when electrowinning of use above-described embodiment 5, embodiment 6, comparative example 5, comparative example 6 carries out electrowinning with anode is as shown in table 9～table 12.
[table 9]
[table 10]
[table 11]
[table 12]
As shown in table 9, in the electrowinning of cobalt, in the situation that use the anode for electrowinning that has formed the embodiment 5 of the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide by the thermolysis of 260 ℃, with respect to using thermolysis by 360 ℃ to form the situation with anode containing the electrowinning of the comparative example 5 of the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide, electrolysis voltage has reduced 0.05V.In addition, as shown in table 10, in the situation that use the anode for electrowinning of embodiment 5, the electrowinning that has formed the comparative example 6 of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with respect to use is used the situation of anode, and electrolysis voltage has reduced 0.02V.; in the situation that use has formed the anode for electrowinning (embodiment 5) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide; the situation that has formed the anode for electrowinning (comparative example 5) of the catalyst layer that contains crystalline state ruthenium oxide and amorphous tantalum oxide with use is compared; electrolysis voltage reduces; in addition; the situation that has formed the anode for electrowinning (comparative example 6) of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with use is compared, and also can further reduce electrolysis voltage.
In addition, as shown in table 11, in the electrowinning of cobalt, in the situation that use the anode for electrowinning that has formed the embodiment 6 of the catalyst layer that contains amorphous ruthenium oxide and amorphous tantalum oxide by the thermolysis of 280 ℃, with respect to using thermolysis by 360 ℃ to form the situation with anode containing the electrowinning of the comparative example 5 of the catalyst layer of crystalline state ruthenium oxide and amorphous tantalum oxide, electrolysis voltage has reduced 0.12V.In addition, as shown in table 12, in the situation that use anode electrowinning for of embodiment 6, formed the situation containing the electrowinning use anode of the comparative example 6 of the catalyst layer of amorphous iridium oxide and amorphous tantalum oxide with respect to use, electrolysis voltage has reduced 0.09V.; in the situation that use has formed the anode for electrowinning (embodiment 6) containing the catalyst layer of amorphous ruthenium oxide and amorphous tantalum oxide; the situation that has formed the anode for electrowinning (comparative example 5) of the catalyst layer that contains crystalline state ruthenium oxide and amorphous tantalum oxide with use is compared; electrolysis voltage reduces; in addition; the situation that has formed the anode for electrowinning (comparative example 6) of the catalyst layer that contains amorphous iridium oxide and amorphous tantalum oxide with use is compared, and also can further reduce electrolysis voltage.
Claims (10)
1. an electrowinning anode, it is the electrowinning of electrolytic solution for using sulfuric acid, it is characterized in that, is formed with the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on conductive base.
2. an electrowinning anode, it is the electrowinning of electrolytic solution for using sulfuric acid, it is characterized in that, be formed with the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide on conductive base, with the anode that is formed with the catalyst layer formed with amorphous tantalum oxide by amorphous iridium oxide on conductive base, compare, more than electrolysis voltage in the time of can making electrowinning reduces 0.02V, perhaps, with the anode that is formed with the catalyst layer formed with amorphous tantalum oxide by the crystalline state ruthenium oxide on conductive base, compare, more than electrolysis voltage in the time of can making electrowinning reduces 0.05V.
3. an electrowinning anode, it is the electrowinning of electrolytic solution for using sulfuric acid, it is characterized in that, is formed with the catalyst layer consisted of amorphous ruthenium oxide and amorphous tantalum oxide on conductive base.
4. the described electrowinning anode of claim 1～3 any one, is characterized in that, in described catalyst layer, the mol ratio of ruthenium and tantalum is 30:70.
5. the described electrowinning anode of claim 1～4 any one, is characterized in that, between described catalyst layer and described conductive base, is formed with middle layer.
6. electrowinning anode claimed in claim 5, is characterized in that, a kind of in the alloy of tantalum, niobium, tungsten, molybdenum, titanium, platinum or the arbitrary metal in them of described middle layer forms.
7. electrowinning anode claimed in claim 5, is characterized in that, described middle layer is containing crystalline state iridium oxide and amorphous tantalum oxide.
8. the described electrowinning anode of claim 1～7 any one, is characterized in that, the metal of electrowinning is any of copper, zinc, nickel, cobalt, platinum, gold and silver, indium, lead, ruthenium, rhodium, palladium, iridium.
9. an electroextraction, it uses sulfuric acid is electrolytic solution, it is characterized in that, right to use requires the described electrowinning of 1～8 any one to extract the metal of expectation with anode.
10. electroextraction claimed in claim 9, is characterized in that, the metal of electrowinning is any of copper, zinc, nickel, cobalt, platinum, gold and silver, indium, lead, ruthenium, rhodium, palladium, iridium.
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| JP2011-067365 | 2011-03-25 | ||
| JP2011067365A JP4916040B1 (en) | 2011-03-25 | 2011-03-25 | Electrolytic sampling anode and electrolytic sampling method using the anode |
| PCT/JP2012/057426 WO2012133136A1 (en) | 2011-03-25 | 2012-03-23 | Anode for electrowinning and electrowinning method using same |
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| US (1) | US20140054180A1 (en) |
| EP (1) | EP2690200B1 (en) |
| JP (1) | JP4916040B1 (en) |
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| AU (1) | AU2012234150B2 (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103797160A (en) * | 2011-09-13 | 2014-05-14 | 学校法人同志社 | Chlorine-generating positive electrode |
| CN109689937A (en) * | 2016-09-09 | 2019-04-26 | 迪诺拉永久电极股份有限公司 | The manufacturing method and alkaline water electrolytic anode of alkaline water electrolytic anode |
| CN111868308A (en) * | 2018-03-07 | 2020-10-30 | 迪诺拉永久电极股份有限公司 | Electrode for electrolysis and method for producing same |
| WO2023208026A1 (en) * | 2022-04-28 | 2023-11-02 | 中国石油化工股份有限公司 | Transition metal-doped iridium-based composite catalyst, and preparation and application thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013029186A1 (en) | 2011-09-01 | 2013-03-07 | Trudel Simon | Electrocatalytic materials and methods for manufacturing same |
| JP5522484B2 (en) * | 2011-09-13 | 2014-06-18 | 学校法人同志社 | Electrolytic plating anode and electrolytic plating method using the anode |
| US9178219B2 (en) * | 2012-12-20 | 2015-11-03 | Ford Global Technologies, Llc | Electrochemical device including amorphous metal oxide |
| US9790605B2 (en) | 2013-06-27 | 2017-10-17 | Yale University | Iridium complexes for electrocatalysis |
| US10081650B2 (en) | 2013-07-03 | 2018-09-25 | Yale University | Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof |
| US20170074823A1 (en) * | 2014-02-12 | 2017-03-16 | The Doshisha | Ion sensor catalyst, ion sensor using same, and quantification method |
| RU2657747C2 (en) * | 2016-04-20 | 2018-06-15 | Общество с ограниченной ответственностью "БИНАКОР-ХТ" (ООО "БИНАКОР-ХТ") | Electrolyzer anode for production of metal alloy powders |
| US11639142B2 (en) | 2019-01-11 | 2023-05-02 | Ford Global Technologies, Llc | Electronic control module wake monitor |
| JP7341395B2 (en) * | 2019-10-30 | 2023-09-11 | 住友金属鉱山株式会社 | Method for recovering copper, nickel, and cobalt from waste lithium-ion batteries |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0090381A1 (en) * | 1982-03-26 | 1983-10-05 | De Nora Permelec S.P.A. | Electrode and method of electrolysis |
| JP2004238697A (en) * | 2003-02-07 | 2004-08-26 | Daiso Co Ltd | Electrode for oxygen generation |
| JP2007146215A (en) * | 2005-11-25 | 2007-06-14 | Daiso Co Ltd | Electrode for oxygen generation |
| WO2009151044A1 (en) * | 2008-06-09 | 2009-12-17 | 学校法人同志社 | Anodes for electrolytic winning of zinc and cobalt and method for electrolytic winning |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61281889A (en) * | 1985-06-06 | 1986-12-12 | Koji Hashimoto | Electrode material for electrolysis |
| JPS6233790A (en) * | 1985-08-02 | 1987-02-13 | Koji Hashimoto | Activated amorphous alloy electrode |
| US5314601A (en) | 1989-06-30 | 1994-05-24 | Eltech Systems Corporation | Electrodes of improved service life |
| JP3463966B2 (en) | 1995-09-25 | 2003-11-05 | 石福金属興業株式会社 | Manufacturing method of electrode for electrolysis |
| US6139705A (en) * | 1998-05-06 | 2000-10-31 | Eltech Systems Corporation | Lead electrode |
| IT1302581B1 (en) * | 1998-10-01 | 2000-09-29 | Nora De | ANODE WITH IMPROVED COATING FOR THE REACTION OF DIOXIDE EVOLUTION IN ELECTROLYTE CONTAINING MANGANESE. |
| US7258778B2 (en) | 2003-03-24 | 2007-08-21 | Eltech Systems Corporation | Electrocatalytic coating with lower platinum group metals and electrode made therefrom |
| AU2005250240B2 (en) * | 2004-06-03 | 2011-06-30 | Rio Tinto Alcan International Limited | High stability flow-through non-carbon anodes for aluminium electrowinning |
| JP2007246987A (en) | 2006-03-16 | 2007-09-27 | Japan Carlit Co Ltd:The | Coating liquid for producing electrode, and electrode for electrolysis produced by using the coating liquid |
| JP2008050675A (en) | 2006-08-28 | 2008-03-06 | Ishifuku Metal Ind Co Ltd | Electrode for electrolysis |
| ITMI20061974A1 (en) | 2006-10-16 | 2008-04-17 | Industrie De Nora Spa | ANODE FOR ELECTROLYSIS |
| BRPI0818104B1 (en) | 2007-11-16 | 2018-11-21 | Akzo Nobel Nv | alkali metal chlorate production process |
| US8022004B2 (en) | 2008-05-24 | 2011-09-20 | Freeport-Mcmoran Corporation | Multi-coated electrode and method of making |
| JP4516618B2 (en) * | 2008-06-23 | 2010-08-04 | 学校法人同志社 | Anode for electrolytic collection of cobalt and electrolytic collection method |
| JP4516617B2 (en) * | 2008-06-09 | 2010-08-04 | 学校法人同志社 | Anode for electrowinning zinc and electrowinning method |
| JP5013438B2 (en) * | 2009-12-08 | 2012-08-29 | 学校法人同志社 | Anode for electrowinning metal and electrowinning method |
-
2011
- 2011-03-25 JP JP2011067365A patent/JP4916040B1/en active Active
-
2012
- 2012-03-23 CN CN201280016122.9A patent/CN103476970B/en not_active Expired - Fee Related
- 2012-03-23 KR KR1020137024065A patent/KR101577664B1/en active IP Right Grant
- 2012-03-23 RU RU2013147642/02A patent/RU2568546C2/en active
- 2012-03-23 US US14/007,488 patent/US20140054180A1/en not_active Abandoned
- 2012-03-23 AU AU2012234150A patent/AU2012234150B2/en not_active Ceased
- 2012-03-23 EP EP12763572.0A patent/EP2690200B1/en active Active
- 2012-03-23 WO PCT/JP2012/057426 patent/WO2012133136A1/en active Application Filing
- 2012-03-23 CA CA2831273A patent/CA2831273C/en not_active Expired - Fee Related
- 2012-03-23 ES ES12763572.0T patent/ES2557194T3/en active Active
-
2013
- 2013-09-25 CL CL2013002745A patent/CL2013002745A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0090381A1 (en) * | 1982-03-26 | 1983-10-05 | De Nora Permelec S.P.A. | Electrode and method of electrolysis |
| JP2004238697A (en) * | 2003-02-07 | 2004-08-26 | Daiso Co Ltd | Electrode for oxygen generation |
| JP2007146215A (en) * | 2005-11-25 | 2007-06-14 | Daiso Co Ltd | Electrode for oxygen generation |
| WO2009151044A1 (en) * | 2008-06-09 | 2009-12-17 | 学校法人同志社 | Anodes for electrolytic winning of zinc and cobalt and method for electrolytic winning |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103797160A (en) * | 2011-09-13 | 2014-05-14 | 学校法人同志社 | Chlorine-generating positive electrode |
| CN103797160B (en) * | 2011-09-13 | 2016-03-16 | 学校法人同志社 | Analyse chlorine anode |
| CN109689937A (en) * | 2016-09-09 | 2019-04-26 | 迪诺拉永久电极股份有限公司 | The manufacturing method and alkaline water electrolytic anode of alkaline water electrolytic anode |
| CN111868308A (en) * | 2018-03-07 | 2020-10-30 | 迪诺拉永久电极股份有限公司 | Electrode for electrolysis and method for producing same |
| CN111868308B (en) * | 2018-03-07 | 2021-07-20 | 迪诺拉永久电极股份有限公司 | Electrode for electrolysis and method for producing same |
| WO2023208026A1 (en) * | 2022-04-28 | 2023-11-02 | 中国石油化工股份有限公司 | Transition metal-doped iridium-based composite catalyst, and preparation and application thereof |
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| ES2557194T3 (en) | 2016-01-22 |
| CA2831273C (en) | 2016-02-23 |
| EP2690200A1 (en) | 2014-01-29 |
| AU2012234150B2 (en) | 2015-07-02 |
| US20140054180A1 (en) | 2014-02-27 |
| EP2690200B1 (en) | 2015-10-07 |
| JP2012201925A (en) | 2012-10-22 |
| JP4916040B1 (en) | 2012-04-11 |
| WO2012133136A1 (en) | 2012-10-04 |
| CN103476970B (en) | 2016-07-06 |
| KR20140002749A (en) | 2014-01-08 |
| CL2013002745A1 (en) | 2014-04-25 |
| AU2012234150A1 (en) | 2013-11-14 |
| RU2568546C2 (en) | 2015-11-20 |
| KR101577664B1 (en) | 2015-12-15 |
| RU2013147642A (en) | 2015-04-27 |
| CA2831273A1 (en) | 2012-10-04 |
| EP2690200A4 (en) | 2014-03-19 |
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