CN104955987A - Selective reductive electrowinning apparatus and methods - Google Patents
Selective reductive electrowinning apparatus and methods Download PDFInfo
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- CN104955987A CN104955987A CN201380048704.XA CN201380048704A CN104955987A CN 104955987 A CN104955987 A CN 104955987A CN 201380048704 A CN201380048704 A CN 201380048704A CN 104955987 A CN104955987 A CN 104955987A
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- anolyte
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- negative electrode
- catholyte
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000002829 reductive effect Effects 0.000 title claims description 33
- 238000005363 electrowinning Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 17
- -1 polyparaphenylene Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
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- 150000001768 cations Chemical class 0.000 claims description 6
- 239000002322 conducting polymer Substances 0.000 claims description 6
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- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000037427 ion transport Effects 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 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
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
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- 150000004679 hydroxides Chemical class 0.000 claims description 3
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 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 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
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- 239000004020 conductor Substances 0.000 description 3
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- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000010814 metallic waste Substances 0.000 description 3
- 229910000967 As alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002835 Pt–Ir Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- OIBMEBLCOQCFIT-UHFFFAOYSA-N ethanesulfonyl fluoride Chemical compound CCS(F)(=O)=O OIBMEBLCOQCFIT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
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- 150000002815 nickel Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/04—Diaphragms; Spacing elements
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A method and electrochemical cell (10) for recovery of metals is provided, where the electrochemical cell (10) includes an anode (30) disposed in an anodic chamber (25), a cathode (20) disposed in a cathodic chamber (15), an ion- conducting separator (35) disposed between the anode (30) and cathode (20) to physically separate the anodic and cathodic chambers (25, 15), a basic pH anolyte (62) containing a sacrificial reductant (60) disposed within the anodic chamber (25), an acidic pH catholyte (52) containing metal ions disposed within the cathodic chamber (15), and an electrical connection (40) between the anode (30) and the cathode (20). The method includes applying a voltage or an electrical current to an electrolytic cell (10) across the cathode (20) and the anode (30) sufficient to reduce the metal ions to form an elemental metal species at the cathode (20), and oxidize the sacrificial reductant (60) at the anode (30).
Description
Related application
This application claims the sequence number submitted on July 26th, 2012 is 61/675,994, title is the rights and interests of the U.S. Provisional Patent Application of " selective reduction electrodeposition equipment and method (SELECTIVE REDUCTIVE ELECTROWINNING APPARATUS AND METHODS) ", and its disclosure is incorporated to herein in full by reference with it.
Technical field
The present invention relates to the recovery of metal ion.Particularly, the present invention relates to the effective electrolysis process utilizing sacrificial reductive agent Footwall drift ion from solution.
Background technology
Such as the metal of nickel, cobalt, chromium, silver, gold, iron, copper, zinc and vanadium is widely used as the alkaline catalysts being suitable for many industrial application and technique, and described industrial application and technique comprise oil manufacture and refining, battery, chemical technique, air venting control etc.During much technique, catalyzer finally will can lose its catalysis, and becomes waste material.In addition, in the electronics industry, the one that these metals represent from circuit card is significantly wasted.
The generation of wrapping metallic waste material (such as used catalyst, battery and circuit card) has become one of main Environmental Problems in these industries, and this is mainly because they are in transport, aftertreatment and the toxicity in the disposal stage be discharged in environment.On the other hand, these metallic scraps comprise the metal of the high part with commercial value.
Expensive for the current process reclaimed and regenerate this metalloid, mainly due to high-energy used up in this kind of recovery process.Such as, electrodeposition is for the typical process from the metallic waste recovery metal of bag.In the process, curtage is applied to electrochemical cell, and anode and negative electrode are immersed in the aqueous solution wrapping metallic waste material in an electrochemical cell.Under applied electric energy, the metal in aqueous solution is reduced at negative electrode place, and water is oxidized at the anode place of electrochemical cell.The high overpotential that this technique is reacted due to Water oxidize and running under high cell voltage.Therefore, the high overpotential of Water oxidize reaction also will cause separating out hydrogen at the cathode compartment of battery, and this reduces the efficiency of metals recovery processes further and affects purity and the quality of institute's salvage material.
Therefore, still demand is existed for effective metals recovery processes.
Summary of the invention
Prerequisite of the present invention is that realize can Footwall drift (metal catalyst such as used) from aqueous solution effectively.More specifically, prerequisite of the present invention utilizes the electrolyzer separated to realize metal ion to be removed effectively from aqueous solution by electrolysis, the ionic conduction barrier film (separator) that described electrolyzer has the alkaline pH anolyte compartment environment comprising sacrificial reductive agent, the acid pH cathode compartment environment comprising the required metal that will be recovered and separated in anolyte compartment and cathode compartment physics.
According to the present invention, the method for Footwall drift comprises voltage or electric current is applied to electrolyzer, and described electrolyzer comprises the anode be arranged in anolyte compartment; Be arranged at the negative electrode in cathode compartment; Be arranged at so that the barrier film separated in anolyte compartment and cathode compartment physics between anode and negative electrode, barrier film allows to carry out ion transport between anolyte compartment and cathode compartment; Be arranged at the anolyte in anolyte compartment, it comprises sacrificial reductive agent, and wherein said anolyte has alkaline ph values; Be arranged at the catholyte in cathode compartment, it comprises at least one or many kinds of metal ions that are dissolved in wherein, and wherein catholyte has acid ph value; And electrical connection (electrical connection) between the anode and cathode.Voltage or electric current are applied to electrolyzer via electrical connection leap negative electrode and anode, wherein said voltage or electric current are enough to reduce described at least one or many kinds of metal ions, to form at least one or more metal element kinds (species) at negative electrode place, and so that at anode place oxidation sacrificial reductive agent.
According to a further embodiment of the invention, electrochemical cell, it comprises anode in the anode compartment; Negative electrode in cathode compartment; Be arranged at so that physics separates the barrier film of anolyte compartment and cathode compartment between anode and negative electrode, described barrier film allows the ion transport between anolyte compartment and cathode compartment; Be arranged at the anolyte in anolyte compartment, it comprises sacrificial reductive agent, and wherein said anolyte has alkaline ph values; Be arranged at the catholyte in cathode compartment, it comprises one or more metal ions be dissolved in wherein, and wherein catholyte has acid ph value; And the electrical connection between anode and negative electrode.
Use for reference the following detailed description and example, will be further understood that object of the present invention and advantage.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the simplification electrolyzer according to the embodiment of the present invention;
Fig. 2 is cyclic voltammogram, and it illustrates and reclaims comparing of nickel by traditional electrodeposition (TE) technique with selective reduction electrodeposition (SRE) technique according to the embodiment of the present invention; And
Fig. 3 is by TE technique and the graphic representation of the electric current (mA) compared according to the chemical property of the SRE technique of the embodiment of the present invention relative to time (second).
Embodiment
Fig. 1 is that the diagram simplifying electrolyzer 10 describes, and it is disposed for flow battery (flow cell) process, to realize Footwall drift from aqueous solution.Simplify electrolyzer 10 and comprise the cathode compartment 15 comprising negative electrode 20, comprise the anolyte compartment 25 of anode 30, wherein said cathode compartment 15 and anolyte compartment 25 by barrier film 35 each other physics separate.But barrier film 35 allows ion to transmit between cathode compartment 15 and anolyte compartment 25, the physical barriers between negative electrode 20 and anode 30 can also be used as simultaneously.Negative electrode 20 and anode 30 are configured with electrical connection 40 betwixt and voltage source (voltage source) 45, and voltage or electric current are supplied to electrochemical cell 10 by voltage source 45.
According to embodiments of the invention, the material solution 50 comprising one or more metal ions for reclaiming becomes at least one component of the catholyte 52 with acid ph value, it flows through cathode compartment 15 by cathode compartment entrance 53 and cathode chamber outlet 55, thus Contact cathod 15.Sacrificial reductive agent 60 becomes at least one component of the anolyte 62 with alkaline ph values, and it flows through anolyte compartment 25 by Anode chamber inlets 63 and anode compartment outlet 63, and contacts anode 30 thus.Optionally, the effluent of cathode compartment 15 and anolyte compartment 25 carries out recirculation by their corresponding re-circulation path 70,80.
According to the present invention, metal is present in raw material 50 with cationic form (i.e. the oxidised form of metal).By way of example, but be not limited to, the metal that can carry out current SRE treatment process includes but not limited to zinc, chromium, tantalum, gallium, iron, cadmium, indium, thallium, cobalt, nickel, tin, lead, copper, bismuth, silver, mercury, chromium, niobium, vanadium, manganese, aluminium and their combination.Therefore, in one embodiment, the metal suitably reclaimed from aqueous solution sample comprises nickel.Therefore, in one embodiment, the metal suitably reclaimed from aqueous solution sample comprises cobalt.Corresponding reduction reaction illustrates as follows:
Reaction formula 1:Ni
+ 2(aq)+2e
-→ Ni (-0.26V vs SHE)
Reaction formula 2:Co
+ 2(aq)+2e
-→ Ni (-0.28V vs SHE)
According to embodiments of the invention, raw material 50 has no particular limits in its metal concentration.Exemplary metal concentration includes but not limited to from about 500ppm and lower, from about 250ppm and lower, from about 100ppm and lower, or from about 50ppm and lower.In addition, the water of the de-metallization obtained from above-mentioned raw materials can have enough low metal concentration to allow directly to be discharged in environment without the need to further process.For denseer material solution, described catholyte 52 can recirculation, until the metallic reducing needed for realizing.
Although do not limit the pH value of material solution 50, according to embodiments of the invention, the pH value of catholyte 52 is acid (namely pH is less than 7).According to an embodiment, the pH value of catholyte 52 is about 3 to about 6.Therefore, in order to reduce pH value, one or more acidic electrolyte baths can with material combination.Exemplary acidic electrolyte bath includes but not limited to boric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their combination.
According to embodiments of the invention, anolyte 62 comprises sacrificial reductive agent, and it reduces the electrochemical potential of electrolyzer effectively.Exemplary sacrificial reductive agent includes but not limited to urea; Ammonia; Ammonium salt; Alcohol, such as ethanol or methyl alcohol, or their combination.Such as, in one embodiment, sacrificial reductive agent 60 can comprise ammonium hydroxide.Sacrificial reductive agent is supplied to anode 30 with the amount exceeding the stoichiometric quantity needed for the metal in catholyte 52.Advantageously, described sacrificial reductive agent can be present in anolyte 62 in excessive more mode, and the sacrificial reductive agent that recirculation is excessive in this process.
According to embodiments of the invention, the pH value of anolyte 62 is alkaline (namely pH value is greater than 7).According to embodiment, the pH value of anolyte 62 is about 9 or larger.Therefore, in order to improve the pH value of anolyte, one or more alkaline electrolytes can combine with sacrificial reductive agent 60.Alkaline electrolyte can be liquid and/or gel.In one embodiment, alkaline electrolyte comprises the hydroxide salt of alkali metal hydroxide or alkaline-earth metal, such as lithium hydroxide, rubidium hydroxide, cesium hydroxide, hydrated barta, strontium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, salt of wormwood and also can use their mixture.Such as, in one embodiment, anolyte 62 can comprise alkaline electrolyte, such as potassium hydroxide.
In substituting embodiment, anolyte 62 can comprise gel, such as solid polymer electrolyte.Suitable alkaline electrolyte gel such as comprises those gels comprising polyacrylic acid, polyacrylic ester, polymethacrylate, polyacrylamide, sulfonated polymer and similar polymkeric substance and multipolymer.Alkaline electrolyte gel can use any suitable method to prepare.One method comprises formation polymkeric substance, is then injected into by oxyhydroxide salt electrolyte in polymkeric substance to form alkaline electrolyte gel or polymeric blends.In other method, can when oxyhydroxide salt electrolyte exists polymerization single polymerization monomer.
Electrode (that is, negative electrode 20 and anode 30) can comprise the carrier that conductor maybe can be coated with greater activity conductor respectively.About negative electrode 20, conductive component is not specifically limited to the conductor of any kind, but conductive component should comprise the substrate (substrate) that metal can be deposited thereon.Such as, the conductive component of negative electrode 20 can comprise carbon, such as carbon fiber, carbon paper, vitreous carbon, carbon nanofiber, carbon nanotube and analogue; Or conducting metal, such as cobalt, copper, iridium, iron, nickel, platinum, palladium, ruthenium, rhodium and their mixture and alloy.The solid support material of negative electrode 20 and/or conductive component should be chosen to compatible with the acidic electrolyte bath of catholyte 52.
According to principle of the present invention, metal ion is reduced at negative electrode 20 place and deposited thereon.In addition, the sedimentation rate of metal is relevant to available surface-area.Therefore, the substrate that surface-area is larger is normally preferred.
According to another principle of the present invention, in the alkaline electrolyte composition or medium of anolyte compartment 25, there is the oxidizing reaction of sacrificial reductive agent at anode 30 place.At anode 30 place in alkaline electrolyte medium, carry out exemplary sacrificial reductive agent urea and the oxidation of ammonia according to following reaction formula:
Reaction formula 3:2NH
3+ 6OH
-→ N
2+ 6H
2o+6e
-(-0.77V vs SHE)
Reaction formula 4:CO (NH
2)
2+ 6OH
-→ N
2+ 5H
2o+CO
2+ 6e
-(-0.034V vs SHE)
Therefore, the conductive component of anode 30 can be to adsorption and oxidation sacrificial reductive agent urea and/or ammonia one or more metals activated.Such as, be included in the common U.S. Patent number 7,485 transferred the possession of to the oxidation of ammonia one or more metals activated, metal disclosed in 211, this patent is incorporated to herein by introducing in full with it.By the mode of other example, available comprise platinum, iridium, ruthenium, rhodium and their combination conductive component carry out the oxidation of ammonia.Conductive component can be used as alloy and/or by several layers of codeposition.
In addition, be included in metal disclosed in the common U.S. Patent Application Publication No. 2009/0095636 transferred the possession of to the activated metal of the oxidation of urea, this patent application is incorporated to herein by introducing in full with it.Such as, available conductive component carries out the oxidation of urea, and described conductive component comprises transition metal, such as nickel; Or precious metal, such as platinum, iridium, ruthenium, rhodium; With their combination.Effective especially metal for urea oxidation comprises nickel and other transition metal.Metal can be used as alloy and/or by several layers of codeposition.In addition, active metal can be in oxidised form, such as hydroxy nickel oxide.
In addition, be included in those metals disclosed in the common U.S. Patent Application Publication No. 2008/0318097 transferred the possession of to the activated metal of oxidation of ethanol and methyl alcohol, this patent application is incorporated to herein in full by reference with it.
The nonrestrictive mode by example, anode 30 can comprise the nickel of galvanic deposit on carbon support, or be formed as pearl and be suspended in the nickel in nickel wire net (gauze), described carbon support is such as carbon fiber, carbon paper, vitreous carbon, carbon nanofiber or carbon nanotube.
A kind of electrode finding that there is the oxidation being beneficial to urea is the nickel electrode (NOMN) of the hydroxy nickel oxide modification of activation.Such as, NOMN electrode can comprise metal base (nickel foil, nickel wire net, titanium foil and titanium wire network), and described metal base uses Watts bath (Watts bath) to be electroplate with Ni.Particularly, nickel coating electrode by be immersed in 33 DEG C containing single nickel salt, sodium acetate and sodium hydroxide solution in and activated.Stainless steel can be used as electrode.By at 6.25A/m
2lower manual polarity switches four cycles of 1 minute and two cycles of 2 minutes, and nickel coating electrode can be used as anode and negative electrode.Finally, electrode can be used as anode remain on identical electric current under and its lower maintenance two hours.The electrode of activation produces the current density higher than M/ nickel, and wherein M represents metal base.
Although the anode with large surface area is favourable, the structure of anode 30 is not limited to any specific shape or form.Such as, conductive component can be formed as paper tinsel, line, silk screen, pearl or be coated on carrier.Suitable anode 30 solid support material can be selected from many known carriers, all like paper tinsels, net and sponge.Solid support material can include but not limited to nickel foil, titanium foil, carbon fiber, carbon paper, vitreous carbon, carbon nanofiber and carbon nanotube.Except these concrete solid support materials listed, other suitable carrier will be admitted by one of ordinary skilled in the art.The conductive component of anode 30 and/or the selection of solid support material should be chosen to compatible with the alkaline electrolyte of anolyte 62.
Barrier film is for dividing cathode compartment 15 and anolyte compartment 25.Barrier film should be made up of the material of the electrolyte composition at chemically resistance to catholyte 52 and anolyte 62.According to embodiment, barrier film comprises cationic conductivity polymkeric substance, it comprises main polymer chain, and described main polymer chain comprises polyether-ether-ketone, polyetherketone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyparaphenylene (polyparaphenylene), polyethylene, polypropylene, polystyrene, fluoropolymer or their combination; With the multiple protonic acid groups being covalently bonded to main polymer chain.Exemplary protonic acid group includes but not limited to sulfonic acid, carbonic acid, phosphoric acid, boric acid or their combination.According to an embodiment, cation conducting polymer comprises the fluoropolymer-multipolymer based on tetrafluoroethylene (sulfonated tetrafluoroethylene-based fluoropolymer-copolymer) of sulfonation; Sulfonation gathers (ether ether ketone); Or sulfonated polyimide.Fluoropolymer-the multipolymer based on tetrafluoroethylene of exemplary sulfonation is 2-[1-[two fluoro-[(trifluoro vinyl) oxygen base] methyl]-1,2,2,2-tetrafluoro oxyethyl group-1,1, polymkeric substance (ethanesulfonyl fluoride, the 2-[1-[difluoro-[(trifluoroethenyl) oxy] methyl]-1 of the fluoro-second sulfonic acid fluoride of 2,2-tetra-and tetrafluoroethylene, 2,2,2-tetrafluoroethoxy]-1,1,2,2 ,-tetrafluoro-, with tetrafluoroethylene).
Electrolyzer can operate under the different range of temperature and pressure.Working pressure can be about normal atmosphere or environmental stress, except the physical restriction of reactor, do not have pressure high limit.Operating temperature range can from the zero pour of about waste water to about 100 DEG C, and can be relevant to the working pressure of electrolyzer.At one atm, in fact service temperature is retained to about 80 DEG C or lower, because be difficult to ammonia to keep in the solution at a higher temperature.Such as, acceptable service temperature can from about 0 DEG C to about 80 DEG C; Or from the scope of about 20 DEG C to about 65 DEG C.More specifically, being useful especially from the service temperature in the scope of about 20 DEG C to about 30 DEG C.
The present invention is not limited to any particular source of electric power.That is, electric power can provide from renewable energy source: wind energy, sun power etc., stores the energy (battery), and traditional grid generation.
But, according to embodiments of the invention, under the voltage difference that the negative electrode 20 of leap electrochemical cell 10 and anode 30 apply remains on certain value, this value is provided for the reduction of metal ion, avoids the oxygen of the hydrogen generation of the essence at negative electrode place or the essence at anode place to produce simultaneously.As used herein, " essence " hydrogen is separated out and " essence " oxygen evolution means that the electric energy being less than about 20% is for generation of on hydrogen and/or oxygen.In other words, alive about 80% or more is executed for removing refuse metal ion.Such as, in one embodiment, the electric energy of about 10% is less than for generation of hydrogen and/or oxygen.In yet another embodiment, the electric energy of about 5% is less than for generation of hydrogen and/or oxygen.In yet another embodiment, the electric energy of about 3% is less than for generation of hydrogen and/or oxygen.In one exemplary embodiment, the voltage that leap negative electrode 20 and anode 30 apply does not produce any hydrogen at negative electrode place.
The voltage difference that leap negative electrode 20 and anode 30 apply can be depending on sacrificial reductive agent and metal to be recovered changes.Such as, use ammonia is reclaimed for nickel as sacrificial reductive agent, is enough at the voltage about between 0.14V and 0.9V, and when urea is used as sacrificial reductive agent, is enough at about 0.66V and the voltage about between 1.1V.According to embodiments of the invention, cross under voltage difference that the negative electrode 20 of the single electrolyzer for reclaiming nickel and anode 30 apply can be maintained at about 1.1 volts or lower voltage.In another exemplary embodiment, the voltage difference of single battery can under the value between about 0.01 volt to about 1.1 volts.In yet another embodiment, the voltage of single battery can under the value of about 0.2 volt to about 0.9 volt.Such as, the metal of such as zinc, chromium, tantalum, gallium, iron, cadmium, indium, thallium, cobalt, nickel, tin, lead, chromium, niobium, vanadium, manganese, aluminium and their combination can use the cell voltage continuing to be no more than about 1.5V to reclaim.Such as, suitable cell voltage includes but not limited to 1.4 volts, 1.3 volts, 1.2 volts or 1.1 volts.
Therefore, according to embodiments of the invention, to contact with negative electrode 20 by making the catholyte 52 containing raw material 50 simultaneously and the anolyte 62 containing sacrificial reductive agent 60 is contacted with the anode 30 of electrochemical cell 10 and realize from raw material 50 Footwall drift.At anode 30 place of electrochemical cell 10, according to reaction formula 3 as discussed above, there is the electrooxidation of sacrificial reductive agent 60 (such as ammonia) in the alkaline electrolyte, simultaneously according to reaction formula 1, there is the reduction of metal species (such as nickel) at negative electrode 20 place of electrochemical cell 10, thus metallic nickel is deposited on negative electrode.
According to foregoing, should it is evident that, electrolysis process disclosed herein is by utilizing sacrificial reductive agent to reduce the high efficiente callback that required electromotive force provides metal.Although the embodiment of Fig. 1 is illustrated as flow battery, principle of the present invention is easily applicable to other configuration, such as batch processing (batch processing).
Use for reference following examples and will be further understood that the present invention.
Embodiment
Artificial battery waste (such as raw material) utilizes NiCl
2simulate.Two experiments are all carried out so that by nickel deposition/be recovered in titanium substrate under the constant potential of 1.3V; Traditional electrodeposition (TE) technique, and the technique of selective reduction electrodeposition (SRE).For TE and SRE technique, negative electrode used is Ti paper tinsel (8cm
2) and the anode that uses be deposited on carbon paper (8cm
2) on Pt-Ir.Utilize
anode and cathode spacer are opened by 117 films.For TE technique, use same solution as catholyte and anolyte, it is the NiCl comprising 0.25M
2, 1M the H of KCl and 30g/L
3bO
4solution.For SRE technique, catholyte is the NiCl comprising 0.25M
2, 1M the H of KCl and 30g/L
3bO
4solution, and anolyte is the NH comprising 1M
4the solution of the KOH of OH and 1M.For electrochemistry reclaim Ni be fixed on 2 hours total time.For TE and SRE technique, measurement quality changes and compares.
As shown in Figure 2, cyclic voltammetry experiment provides and uses traditional electrodeposition (TE) technique with selective reduction electrodeposition (SRE) technique of the present invention to reclaim comparing of nickel.When compared with TE technique, the cell voltage for the SRE technique reclaiming nickel is reduced to 0.54 volt from 2.35 volts, and this represents the energy consumption of reduction by 77%.As shown in table 1, in all variablees affecting nickel cost recovery, SRE technique is better than TE technique.
Table 1: traditional electrodeposition (TE) technique compares with selective reduction electrodeposition (SRE) technique.
As shown in Figure 3, under applied voltage, observe the electric current of essence in SRE technique, this shows that the recovery of nickel metal in SRE technique under applied voltage is feasible.On the contrary, for TE technique, electric current is very low, is thus infeasible or unpractiaca for TE technique under applied voltage.After operation 2 hours, during SRE technique, reclaim the nickel of 11.5 milligrams in the cathode, and be not recovered to nickel in TE technique.
Although by the description of one or more embodiment to inventions have been explanation, although and described in detail embodiment, they not intention by the restriction of the scope of claims or be restricted to such details by any way.Extra advantage and modification will easily manifest for those technician in this area.Therefore the present invention is not limited to shown and described specific detail, representational product and method and exemplary embodiment at it widely.Therefore, such details can be deviated from when not departing from general inventive concept.
Claims (20)
1. the method for Footwall drift, it comprises:
Voltage or electric current are applied to electrolyzer, and described electrolyzer comprises:
Be arranged at the anode in anolyte compartment;
Be arranged at the negative electrode in cathode compartment;
Be arranged at so that the barrier film separated in described anolyte compartment and described cathode compartment physics between described anode and described negative electrode, described barrier film allows the ion transport between described anolyte compartment and described cathode compartment;
Be arranged at the anolyte in described anolyte compartment, described anolyte comprises sacrificial reductive agent, and wherein said anolyte has alkaline ph values;
Be arranged at the catholyte in described cathode compartment, described catholyte comprises at least one or many kinds of metal ions that are dissolved in wherein, and wherein said catholyte has acid ph value; And
Electrical connection between described anode and described negative electrode, wherein said voltage or described electric current are applied to described electrolyzer via the described electrical connection described negative electrode of leap and described anode, wherein said voltage or described electric current are enough to reduce described at least one or many kinds of metal ions, to form at least one or more metal element kinds at described negative electrode place, and to be oxidized described sacrificial reductive agent at described anode place.
2. method according to claim 1, is characterized in that, described voltage or electric current are less than the generation of impact in the essence of described negative electrode place hydrogen and/or the value needed for the generation in the essence of described anode place oxygen.
3. method according to claim 1, is characterized in that, described sacrificial reductive agent is selected from the group be made up of urea, ammonia, ethanol, methyl alcohol and their combination.
4. method according to claim 1, is characterized in that, described barrier film comprises cation conducting polymer, and described cation conducting polymer comprises:
Main polymer chain, described main polymer chain comprises polyether-ether-ketone, polyetherketone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyparaphenylene, polyethylene, polypropylene, polystyrene, fluoropolymer, or their combination; With
Be covalently bonded to multiple protonic acid groups of described main polymer chain.
5. method according to claim 1, is characterized in that, described anode or described negative electrode comprise independently selected from the material in the group be made up of cobalt, copper, iron, nickel, platinum, iridium, ruthenium, rhodium and their mixture and their alloy.
6. method according to claim 1, is characterized in that, described anode comprises solid support material further, and described solid support material is laminated with one or more metals, metal mixture or alloy at least in part.
7. method according to claim 1, is characterized in that, described anolyte comprises alkaline electrolyte composition.
8. method according to claim 7, it is characterized in that, described alkaline electrolyte composition comprises hydroxide salt, and described hydroxide salt is selected from by following formed group: lithium hydroxide, rubidium hydroxide, cesium hydroxide, hydrated barta, strontium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, salt of wormwood, sodium carbonate and their mixture.
9. method according to claim 7, is characterized in that, described alkaline electrolyte composition comprises polymer gel.
10. method according to claim 9, is characterized in that, described polymer gel comprises polyacrylic acid, polyacrylic ester, polymethacrylate, polyacrylamide, sulfonated polymer or their combination.
11. methods according to claim 1, it is characterized in that, described at least one or many kinds of metal ions are selected from the positively charged ion by the metal of following formed group: zinc, chromium, tantalum, gallium, iron, cadmium, indium, thallium, cobalt, nickel, tin, lead, copper, bismuth, silver, mercury, gold, chromium, niobium, vanadium, manganese, aluminium and their combination
12. methods according to claim 1, is characterized in that, the pH of described anolyte is about 8 or higher.
13. methods according to claim 1, is characterized in that, described electrolyzer is operating to the temperature within the scope of about 80 DEG C from about 0 DEG C.
14. methods according to claim 1, is characterized in that, described anolyte compartment comprises the first entrance and the first outlet further, and described method also comprises:
Described anolyte is made to flow in described anolyte compartment by described first entrance;
Be oxidized at least part of described sacrificial reductive agent in described anolyte to form the anolyte of modification;
The anolyte of described modification is discharged from described anolyte compartment by described first outlet; And
Optionally, make the anolyte of described modification recirculated through described anolyte compartment.
15. methods according to claim 1, is characterized in that, described cathode compartment comprises the second entrance and the second outlet further, and described method also comprises:
Described catholyte is made to flow in described cathode compartment by described second entrance;
Be reduced to the described at least one of small part or many kinds of metal ions to form at least one or more metal element kinds, thus form the catholyte of modification;
The catholyte of described modification is discharged from described cathode compartment by described second outlet; And
Optionally, make the catholyte of described modification recirculated through described cathode compartment.
16. electrochemical cells, it comprises:
Anode in the anode compartment;
Negative electrode in the cathodic compartment;
Be arranged at so that physics separates the barrier film of described anolyte compartment and described cathode compartment between described anode and described negative electrode, described barrier film allows the ion transport between described anolyte compartment and described cathode compartment;
Be arranged at the anolyte in described anolyte compartment, it comprises sacrificial reductive agent, and wherein said anolyte has alkaline ph values;
Be arranged at the catholyte in described cathode compartment, it comprises one or more metal ions be dissolved in wherein, and wherein said catholyte has acid ph value; And
Electrical connection between described anode and described negative electrode.
17. electrochemical cells according to claim 16, it is characterized in that, described barrier film comprises cation conducting polymer, described cation conducting polymer comprises:
Main polymer chain, described main polymer chain comprises polyether-ether-ketone, polyetherketone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyparaphenylene, polyethylene, polypropylene, polystyrene, fluoropolymer or their combination; And
Be covalently bonded to multiple protonic acid groups of described main polymer chain.
18. electrochemical cells according to claim 17, is characterized in that, described protonic acid group is selected from the group be made up of sulfonic acid, carbonic acid, phosphoric acid or boric acid.
19. electrochemical cells according to claim 17, is characterized in that, described cation conducting polymer comprises the fluoropolymer-multipolymer based on tetrafluoroethylene of sulfonation; Sulfonation gathers (ether ether ketone); Or sulfonated polyimide.
20. electrochemical cells according to claim 19, it is characterized in that, fluoropolymer-the multipolymer based on tetrafluoroethylene of described sulfonation is 2-[1-[two fluoro-[(trifluoro vinyl) oxygen base] methyl]-1,2,2,2-tetrafluoro oxyethyl group-1,1, the polymkeric substance of the fluoro-second sulfonic acid fluoride of 2,2-tetra-and tetrafluoroethylene.
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| US61/675,994 | 2012-07-26 | ||
| US13/802,919 US20140027301A1 (en) | 2012-07-26 | 2013-03-14 | Selective reductive electrowinning apparatus and method |
| US13/802,919 | 2013-03-14 | ||
| PCT/US2013/050601 WO2014018302A1 (en) | 2012-07-26 | 2013-07-16 | Selective reductive electrowinning apparatus and methods |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477159A (en) * | 2016-06-30 | 2019-03-15 | 小利兰·斯坦福大学托管委员会 | For extraction/removal metal ion electrochemical deposition from water |
| CN109534455A (en) * | 2018-11-09 | 2019-03-29 | 西安交通大学 | A kind of electrochemical method of low-consumption high-efficiency processing heavy metal wastewater thereby |
| CN109609974A (en) * | 2019-01-29 | 2019-04-12 | 长江师范学院 | Conducive to the method for reducing Zinc electrolysis tank voltage and energy consumption |
| CN110747487A (en) * | 2019-11-12 | 2020-02-04 | 上海莒纳新材料科技有限公司 | Water electrolysis oxygen generation system and air quality control system of closed space |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11735756B2 (en) | 2020-11-16 | 2023-08-22 | Cougar Creek Technologies, Llc | Redox flow battery systems and methods utilizing a temporal energy profile |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4330377A (en) * | 1980-07-10 | 1982-05-18 | Vulcan Materials Company | Electrolytic process for the production of tin and tin products |
| CA1214178A (en) * | 1984-03-14 | 1986-11-18 | Jagabandhu Das | 7-oxabicycloheptane substituted prostaglandin interphenylene analogs |
| CN1922343A (en) * | 2004-02-26 | 2007-02-28 | 爱托特奇德国股份有限公司 | Baths, systems and processes for electroplating zinc-nickel ternary and higher alloys and articles so electroplated |
| US20110243823A1 (en) * | 2010-04-02 | 2011-10-06 | Ohio University | Selective Catalytic Reduction Via Electrolysis of Urea |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE24865E (en) * | 1960-09-06 | Ion exchange materials and method of | ||
| BE594986A (en) * | 1959-09-28 | |||
| JPS5819752B2 (en) * | 1974-03-30 | 1983-04-19 | カガクギジユツチヨウ キンゾクザイリヨウギジユツケンキユウシヨチヨウ | dodenkaihou |
| US4279711A (en) * | 1980-01-21 | 1981-07-21 | Vining Paul H | Aqueous electrowinning of metals |
| CA1214748A (en) * | 1982-08-11 | 1986-12-02 | Inco Limited | Process for nickel electroreplenishment for nickel refinery electrolyte |
| US4632738A (en) * | 1982-09-03 | 1986-12-30 | Great Central Mines Ltd. | Hydrometallurgical copper process |
| US4431496A (en) * | 1982-09-07 | 1984-02-14 | Institute Of Gas Technology | Depolarized electrowinning of zinc |
| US4460444A (en) * | 1983-04-06 | 1984-07-17 | Westinghouse Electric Corp. | Hydriodic acid-anode-depolarized hydrogen generator |
| US4627899A (en) * | 1985-02-15 | 1986-12-09 | The United States Of America As Represented By The Secretary Of The Interior | Electrolytic cell and methods combining electrowinning and electrochemical reactions employing a membrane or diaphragm |
| US4752364A (en) * | 1986-05-19 | 1988-06-21 | Delphi Research, Inc. | Method for treating organic waste material and a catalyst/cocatalyst composition useful therefor |
| US4699700A (en) * | 1986-05-19 | 1987-10-13 | Delphi Research, Inc. | Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor |
| DE4035316C2 (en) * | 1990-11-07 | 1993-11-04 | Daimler Benz Ag | METHOD FOR ELECTROLYTIC RECOVERY OF NICKEL FROM CHLORIDE-CONTAINING ELECTROLYTIC BATHS |
| US8216437B2 (en) | 2003-10-10 | 2012-07-10 | Ohio University | Electrochemical cell for oxidation of ammonia and ethanol |
| WO2005035444A2 (en) | 2003-10-10 | 2005-04-21 | Ohio University | Electro-catalysts for the oxidation of ammonia in alkaline media |
| US8303781B2 (en) | 2007-10-15 | 2012-11-06 | Ohio University | Electrolytic cells and methods for the production of ammonia and hydrogen |
-
2013
- 2013-03-14 US US13/802,919 patent/US20140027301A1/en not_active Abandoned
- 2013-07-16 EP EP13744888.2A patent/EP2877613B1/en active Active
- 2013-07-16 CN CN201380048704.XA patent/CN104955987A/en active Pending
- 2013-07-16 WO PCT/US2013/050601 patent/WO2014018302A1/en active Application Filing
- 2013-07-16 CA CA2879727A patent/CA2879727A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4330377A (en) * | 1980-07-10 | 1982-05-18 | Vulcan Materials Company | Electrolytic process for the production of tin and tin products |
| CA1214178A (en) * | 1984-03-14 | 1986-11-18 | Jagabandhu Das | 7-oxabicycloheptane substituted prostaglandin interphenylene analogs |
| CN1922343A (en) * | 2004-02-26 | 2007-02-28 | 爱托特奇德国股份有限公司 | Baths, systems and processes for electroplating zinc-nickel ternary and higher alloys and articles so electroplated |
| US20110243823A1 (en) * | 2010-04-02 | 2011-10-06 | Ohio University | Selective Catalytic Reduction Via Electrolysis of Urea |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477159A (en) * | 2016-06-30 | 2019-03-15 | 小利兰·斯坦福大学托管委员会 | For extraction/removal metal ion electrochemical deposition from water |
| CN109534455A (en) * | 2018-11-09 | 2019-03-29 | 西安交通大学 | A kind of electrochemical method of low-consumption high-efficiency processing heavy metal wastewater thereby |
| CN109609974A (en) * | 2019-01-29 | 2019-04-12 | 长江师范学院 | Conducive to the method for reducing Zinc electrolysis tank voltage and energy consumption |
| CN110747487A (en) * | 2019-11-12 | 2020-02-04 | 上海莒纳新材料科技有限公司 | Water electrolysis oxygen generation system and air quality control system of closed space |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2877613A1 (en) | 2015-06-03 |
| CA2879727A1 (en) | 2014-01-30 |
| EP2877613B1 (en) | 2018-03-28 |
| WO2014018302A1 (en) | 2014-01-30 |
| US20140027301A1 (en) | 2014-01-30 |
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