EP2872673B1 - Cellule électrolytique dépourvue de séparateur et son utilisation - Google Patents
Cellule électrolytique dépourvue de séparateur et son utilisation Download PDFInfo
- Publication number
- EP2872673B1 EP2872673B1 EP13735335.5A EP13735335A EP2872673B1 EP 2872673 B1 EP2872673 B1 EP 2872673B1 EP 13735335 A EP13735335 A EP 13735335A EP 2872673 B1 EP2872673 B1 EP 2872673B1
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- European Patent Office
- Prior art keywords
- anode
- electrolyte
- electrolytic cell
- cathode
- electrolysis
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- 239000003792 electrolyte Substances 0.000 claims description 87
- 238000005868 electrolysis reaction Methods 0.000 claims description 76
- 229910003460 diamond Inorganic materials 0.000 claims description 47
- 239000010432 diamond Substances 0.000 claims description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 16
- 229910052758 niobium Inorganic materials 0.000 claims description 15
- 239000010955 niobium Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001247 metal acetylides Chemical class 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 86
- 238000000034 method Methods 0.000 description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 36
- 230000008569 process Effects 0.000 description 27
- 239000008151 electrolyte solution Substances 0.000 description 24
- 229940021013 electrolyte solution Drugs 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 23
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 125000005385 peroxodisulfate group Chemical group 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- -1 ammonium ions Chemical class 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 5
- 210000004379 membrane Anatomy 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010349 cathodic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/29—Persulfates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
Definitions
- the present invention relates to an electrolysis cell and its use for producing an ammonium or alkali metal peroxodisulfate.
- sodium peroxodisulfate is produced with a current efficiency of 70 to 80% in an electrolysis cell with a cathode protected by a diaphragm and a platinum anode by adding a neutral aqueous anolyte solution with an initial content of 5 to 9% by weight of sodium ions, 12 to 30% by weight Sulfate ions, 1 to 4% by weight ammonium ions, 6 to 30% by weight peroxodisulfate ions and a potential-increasing promoter, such as, in particular, thiocyanate Using a sulfuric acid solution as a catholyte at a current density is electrolyzed by at least 0.5 to 2 A / cm 2 . After the peroxodisulfate has crystallized out and separated off from the anolyte, the mother liquor is mixed with the cathode product, neutralized and fed back to the anode.
- a neutral aqueous anolyte solution with an initial content of 5
- EP-B 0 428 171 discloses a filter press type electrolytic cell for the production of peroxo compounds including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate. Platinum foils applied hot isostatically to a valve metal are used as anodes. A solution of the corresponding sulfate containing a promoter and sulfuric acid is used as the anolyte. This method also has the aforementioned problems.
- Peroxodisulfates are produced by anodic oxidation of an aqueous solution containing neutral ammonium sulfate.
- the solution obtained from the anodic oxidation which contains ammonium peroxodisulfate, is reacted with sodium hydroxide solution or potassium hydroxide solution.
- the mother liquor is recycled in a mixture with the catholyte produced in the electrolysis. In this process, too, the electrolysis takes place in the presence of a promoter on a platinum electrode as the anode.
- the international patent application WO 2011/066632 describes, in connection with the purification of water, a cylindrical electrolysis cell which each comprises a tubular cathode and anode, the anode comprising a conductive support coated with a conductive diamond layer. There are also inlet pipes, outlet pipes and, if necessary, a diaphragm to separate the electrolyte space.
- the electrolysis cell is specially designed for the processing of wastewater and accordingly not designed for high solid concentrations in the electrolyte solution. Distribution facilities are not available.
- the object of the present invention is to provide an electrolysis cell which can be used in a technical process for the production of ammonium and alkali metal peroxodisulfates, the disadvantages of the known processes being able to be avoided or at least only occurring to a lesser extent.
- Also described herein is a process for the preparation of an ammonium or alkali metal peroxodisulfate comprising anodic oxidation of a salt from the series ammonium sulfate, alkali metal sulfate and / or the corresponding aqueous electrolyte containing hydrogen sulfate in an electrolytic cell, comprising at least one anode and one cathode, wherein a diamond layer arranged on a conductive support and doped with a trivalent or pentavalent element is used as the anode, wherein the electrolysis cell comprises an undivided electrolysis space between the anode and the cathode and the aqueous electrolyte does not contain a promoter for increasing the decomposition voltage from water to oxygen.
- the salt used for the anodic oxidation from the series ammonium sulfate, alkali metal sulfate and / or the corresponding hydrogen sulfates can be any desired alkali metal sulfate or corresponding hydrogen sulfate.
- the use of sodium and / or potassium sulfate and / or the corresponding hydrogen sulfate is possible.
- Promoter or also “polarizer” in the context of the present application is any agent which is known to the person skilled in the art as an additive when carrying out an electrolysis to increase the decomposition voltage of water to oxygen or to improve the current yield.
- An example of such a promoter used in the prior art is thiocyanate, such as, for example, sodium or ammonium thiocyanate. Such a promoter is not used in the process described. In other words, in the method described herein, the electrolyte has a promoter concentration of 0 g / l.
- an anode which comprises a diamond layer arranged on a conductive support and doped with a 3- or 5-valent element.
- One advantage of this feature is the very high wear resistance of the diamond coating. Long-term tests have shown that such electrodes have a minimum life of more than 12 years.
- the anode used can be of any shape.
- the carrier material can be selected be out of the group consisting of silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements and / or aluminum or combinations of the elements.
- the cathode used in the method described herein is preferably made of lead, carbon, tin, platinum, nickel, alloys of these elements, zirconium and / or acid-resistant stainless steels, as they are known to the person skilled in the art.
- the cathode can have any spatial configuration.
- the electrolyte space between the anode and cathode is undivided, i.e. there is no separator between anode and cathode.
- the use of an undivided cell enables electrolyte solutions with very high solids concentrations, which in turn significantly reduces the energy expenditure in salt production, essentially crystallization and water evaporation, in direct proportion to the increase in the solids content, but at least to 25% of that of a divided cell.
- the method described is carried out in a three-dimensional cell.
- the cell is designed as a tubular cell.
- a tube geometry i.e. a tube cell, Consisting of an inner tube as the anode, preferably made of diamond-coated niobium, and an outer tube as the cathode, preferably made of acid-resistant stainless steel, is an advantageous construction with low material costs.
- the use of an annular gap as a common electrolyte space leads to a uniform and thus low flow loss Flow through and thus a high utilization of the available electrolysis surfaces, which in turn means a high current yield.
- the production costs of such a cell are low compared to a so-called flat cell.
- electrolysis cells can be combined, preferably in the form of a double tube package.
- the electrolyte used preferably has an acidic, preferably sulfuric acid, or neutral pH.
- the electrolyte can be circulated through the electrolytic cell during the process. This prevents an undesirable high electrolyte temperature in the cell, which accelerates the decomposition of the persulfates.
- the method can include discharging electrolyte solution from the electrolyte circuit. This can be done in particular to obtain peroxodisulfate produced.
- a further aspect therefore relates to the recovery of generated peroxodisulfates by crystallization and separation of the crystals from the electrolyte solution with the formation of an electrolyte solution, the electrolyte solution preferably being removed from the electrolyte circuit beforehand was discharged.
- a recirculation of the electrolyte mother liquor is possible, especially if before generated peroxodisulfates were separated, with increasing the content of acid, sulfate and / or hydrogen sulfate in the electrolysis cell.
- the anodic oxidation can be carried out at an anodic current density of 50-1500 mA / cm 2, in particular about 50-1200 mA / cm 2 .
- a current density used particularly preferably is in the range from 60-975 mA / cm 2 .
- the electrolyte used preferably has a total solids content of about 0.5 to 650 g / l.
- the (working) electrolyte preferably contains about 100 to about 500 g / l persulfate, more preferably about 150 to about 450 g / l persulfate and most preferably 250-400 g / l persulfate.
- the method thus enables high solids concentrations in the electrolyte solution in particular, without the addition of a potential-increasing agent or promoter and the resulting requirements for exhaust gas and wastewater treatment with high current yields in the peroxodisulfate production at the same time.
- the electrolyte solution preferably contains from about 0.1 to about 3.5 mol of sulfuric acid per liter (l) of electrolyte solution, more preferably 1-3 mol of sulfuric acid per liter of electrolyte solution, and most preferably 2.2-2.8 mol of sulfuric acid per liter of electrolyte solution.
- an electrolyte with the following composition is particularly preferably used in the process described herein: 150 to 500 g of persulfate and 0.1 to 3.5 mol of sulfuric acid per mol of electrolyte solution per liter of electrolyte.
- the total solids content is preferably 0.5 g / l to 650 g / l, more preferably 100-500 g / l and most preferably 250-400 g / l, the sulphate content being variable.
- the promoter portion is 0 g / l.
- the invention relates to a built up from individual components, Undivided electrolysis cell, an electrolysis device composed of several such electrolysis cells, and its use for the oxidation of an electrolyte, as defined in the claims.
- Electrolysis is understood to mean a chemical change caused by the passage of current through an electrolyte, which is expressed in a direct conversion of electrical energy into chemical energy through the mechanism of electrode reactions and ion migration.
- the technically most important electrochemical conversion is the electrolysis of saline solution, which produces caustic soda and chlorine gas.
- the production of inorganic peroxides is nowadays carried out on an industrial scale in electrolysis cells.
- the reactions can be carried out at high concentrations of starting materials and corresponding products.
- High product concentrations ensure that the end product is easy to work up, since the solvent must be removed if the reaction products are in solution.
- the energy consumption of the downstream processing of the electrolysis products can thus also be reduced.
- anode and cathode materials must also meet the mechanical requirements at high solids concentrations and therefore be extremely wear-resistant.
- the electrolysis cells In order to make the electrolysis as economical as possible, the electrolysis cells must be designed so that the electrolysis can be carried out at the highest possible current densities. This is only possible if the anode and cathode have good electrical conductivity and are chemically inert to the electrolyte. Usually graphite or platinum is used as anode material. However, these materials have the disadvantage that they do not have sufficient abrasion resistance at high solids concentrations.
- Electrodes are coated with an electrically conductive diamond layer, the diamond layer being applied using a chemical vapor deposition (CVD) process.
- CVD chemical vapor deposition
- the object of the present invention is to provide an electrolysis cell which enables a continuous and optimized electrolysis process at high solids concentrations (up to about 650 g / l) and at high current density ranges (up to about 1500 mA / cm 2 ).
- the electrolysis cell should be adapted to the electrochemical reactions to be carried out and individual components should be able to be exchanged easily without the actual cell body being destroyed.
- the anode and cathode are arranged concentrically to one another, so that - the electrolyte space is formed as an annular gap between the inner anode and the outer cathode.
- - - The diameter of the cathode is therefore larger than that of the anode.
- the electrolyte space does not contain a membrane or a diaphragm.
- it is an electrolysis cell with a common electrolyte space, i. the electrolysis cell is undivided.
- the distance between the anode outer surface and the cathode inner surface is preferably between 1-20 mm, more preferably between 1-15 mm, even more preferably between 2-10 mm and most preferably between 2-6 mm.
- the inner diameter of the cathode is preferably between 10-400 mm, more preferably between 20-300 mm, even more preferably between 25-250 mm.
- the anode and cathode are each independently between 20-120 cm, more preferably between 25-75 cm long.
- the length of the electrolyte space is preferably at least 20 cm, more preferably at least 25 cm, and at most preferably 120 cm, more preferably 75 cm.
- the cathode used according to the invention is preferably made of lead, carbon, tin, platinum, nickel, alloys of these elements, zirconium and / or iron alloys, in particular made of stainless steel, in particular acid-resistant stainless steel.
- the cathode is made of acid-resistant stainless steel.
- the base material of the rod-shaped or tubular, preferably tubular, anode is preferably silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements, and / or aluminum, or combinations of the elements.
- the anode support material can be identical to the anode base material or different.
- the anode base material functions as a conductive carrier.
- Any desired conductive material known to the person skilled in the art can be used as the conductive carrier.
- Particularly preferred carrier materials are silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements, and / or aluminum, or combinations of the elements. Silicon, titanium, niobium, tantalum, tungsten or carbides of these elements, more preferably niobium or titanium, even more preferably niobium, are particularly preferably used as the conductive support.
- a conductive diamond layer is applied to this carrier material.
- the diamond layer can be doped with at least one 3-valent or at least one 5-valent main or sub-group element.
- the doped diamond layer is thus an n-conductor or a p-conductor. It is preferred here that a boron-doped and / or phosphorus-doped diamond layer is used.
- the amount of doping is set in such a way that the desired, usually just sufficient, conductivity is achieved.
- the crystal structure can contain up to 10,000 ppm, preferably from 10 ppm to 2000 ppm, boron and / or phosphorus.
- the diamond layer can be applied over the entire surface or in sections, preferably on the entire outer surface of the rod-shaped or tubular anode.
- the conductive diamond layer is preferably free of pores.
- the diamond electrodes can be produced in two special CVD (Chemical Vapor Deposition) processes. These are the microwave plasma CVD and hot wire CVD processes. In both cases, the gas phase, which is activated to the plasma by microwave irradiation or thermally by hot wires, is made up of methane, hydrogen and possibly other additives, in particular a gaseous compound of the dopant.
- CVD Chemical Vapor Deposition
- a p-type semiconductor By using the boron compound such as trimethyl boron, a p-type semiconductor can be provided. Using a gaseous phosphorus compound as a dopant, an n-type semiconductor is obtained. By depositing the doped diamond layer on crystalline silicon, a particularly dense and pore-free layer is obtained.
- the diamond layer is preferably applied in a film thickness of about 0.5-5 ⁇ m, preferably about 0.8-2.0 ⁇ m and particularly preferably about 1.0 ⁇ m to the conductive carrier used according to the invention. In another embodiment, the diamond layer is preferably applied in a film thickness of 0.5-35 ⁇ m, preferably 5-25 ⁇ m, most preferably 10-20 ⁇ m, to the conductive support used according to the invention.
- the deposition can also take place on a self-passivating metal such as titanium, tantalum, tungsten, or niobium.
- a self-passivating metal such as titanium, tantalum, tungsten, or niobium.
- PA Michaud Electrochemical and Solid State Letters, 3 (2) 77-79 (2000 ) referenced.
- anode comprising a niobium or titanium support with a boron-doped diamond layer, in particular with a diamond layer doped with up to 10,000 ppm boron, is particularly preferred.
- the diamond-coated electrodes are characterized by a very high mechanical strength and abrasion resistance.
- the anode and / or the cathode is preferably connected to the power source via the distributor device.
- the distributor device In the event that the anode and cathode are connected to the power source via the distributor device, it must be ensured that the distributor device is electrically insulated accordingly. In any case, good electrical contact between the anode and / or cathode and the distributor device must be ensured.
- the distributor device also ensures a homogeneous feed of the electrolyte from the feed pipe into the electrolyte space. After the electrolyte has passed the electrolyte compartment, the converted electrolyte (electrolysis product) is effectively collected with the help of at least one upstream distributor and discharged via a drain pipe.
- the distributor devices according to the invention preferably consist, independently of one another, of silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements and / or aluminum or combinations of the elements, particularly preferably of titanium.
- the distributor devices have at least one connection point for at least one outlet or inlet pipe and one connection point for the anode. Forms the connection point for the anode a possibly closed hollow cylinder that is flush with the anode tube or -staff completes.
- the hollow cylinder in the distributor device can seal the anode tube tightly so that no electrolyte can get into the interior of the anode.
- the connection point of the distributor device to the anode can have a relief bore in the anode tube. This prevents electrolyte from flowing off into the anode tube if the pressure on the distributor element is too high.
- the optionally closed hollow cylinder of the distributor device can be attached to the carrier material of the anode or directly to the diamond-coated carrier. In the latter case, the carrier and the distributor device are separated from one another by the conductive diamond layer.
- the distributor device is irreversibly connected to the anode, particularly preferably welded. This is particularly advantageous when working with high currents.
- the anode and the distributor device can be welded by diffusion welding, electron beam welding or laser welding.
- Radial bores are distributed over the circumference of the hollow cylinder of the distributor device.
- the distributor device preferably has 3, more preferably 4 and even more preferably 5 radial bores. Through the radial bores in the distributor device, the electrolyte can be distributed homogeneously and in a streamlined manner into the electrolyte space and, after passing through the electrolyte space, the electrolysis product can be effectively removed.
- the electrolyte is fed to the electrolysis cell and the distributor device via the feed pipe.
- the electrolysis product is discharged from the electrolysis cell via the drain pipe after the electrolysis product has been collected in the distributor device.
- the distributor device is designed in such a way that it also tightly seals the tubular cathode so that no electrolyte or electrolysis product can escape from the cathode.
- anode, cathode, distributor device, inlet and outlet pipe can be assembled to form an electrolysis cell using appropriate assembly devices known to those skilled in the art.
- the individual components can be made of different materials and can be exchanged or replaced individually if damaged. It has thus succeeded in a simple way to connect the diamond anode according to the invention and the other components, which are made from cheaper materials, to one another to form an electrolysis cell which is very compact in design.
- the tubular electrolytic cell is also characterized by high Strength while using little material. Parts that wear out over time due to the abrasive electrolytes, for example, can be replaced individually, so that economical use of materials is guaranteed in this respect as well.
- the flow is favorable to the electrolyte space, which prevents flow losses and the surface is optimally used for the electrochemical exchange of substances.
- a continuous and homogeneous electrolysis process with high solids concentrations and current density ranges is possible due to the electrode materials and electrode arrangement.
- Another aspect of the present invention is an electrolysis device which comprises at least two electrolysis cells according to the invention, wherein the electrolyte passes through the electrolysis cells one after the other and the electrolysis cells are operated in an electrochemically connected parallel.
- the system services can be implemented flexibly and without limits.
- the electrolysis cell according to the invention or the electrolysis device according to the invention is particularly suitable for oxidizing an electrolyte.
- the undivided electrolysis cell is particularly suitable for the oxidation of an electrolyte when neither the electrolyte nor the electrolysis product, which are produced or converted at the anode or cathode, are disruptively altered by the other electrode process or react with one another.
- the electrolysis cells according to the invention can be operated with a current density between 50-1500 mA / CM 2 , preferably 50-1200 mA / cm 2 , more preferably 60-975 mA / cm 2 and thus enable large-scale and economical processes.
- the electrolysis cells / electrolysis devices according to the invention can also be used at very high solids contents between 0.5-650 g / l, preferably 100-500 g / l, more preferably 150-450 g / l and even more preferably 250-400 g / l can be used.
- the electrolysis cells / devices according to the invention are particularly suitable for the anodic oxidation of sulfate to peroxodisulfate.
- electrolysis cells / electrolysis devices according to the invention have proven themselves in particular for the production of peroxodisulfates, for example in a method described herein.
- the electrolyte space between the anode and cathode is undivided, i.e. there is no separator between anode and cathode.
- the use of an undivided cell enables electrolyte solutions with very high solids concentrations, which in turn significantly reduces the energy expenditure in salt production, essentially crystallization and water evaporation, in direct proportion to the increase in the solids content, but at least to 25% of that of a divided cell.
- the use of a promoter is also not necessary.
- the electrolyte used preferably has an acidic, preferably sulfuric acid, or neutral pH.
- the electrolyte can be circulated through the electrolytic cell during the process. This prevents an undesirable high electrolyte temperature in the cell, which accelerates the decomposition of the persulphates.
- the electrolyte solution is discharged from the electrolyte circuit to recover the peroxodisulfate produced.
- the peroxodisulfate produced can be obtained by crystallization and separation of the crystals from the electrolyte solution to form an electrolyte liquor.
- the electrolyte used preferably has a total solids content of about 0.5 to 650 g / l at the start of the electrolysis.
- the electrolyte preferably contains from about 100 to about 500 g / l sulfate, more preferably from about 150 to about 450 g / l sulfate, and most preferably from 250-400 g / l sulfate at the start of the reaction.
- the use of the electrolysis cell / device according to the invention thus enables high solids concentrations in the electrolyte solution, without the addition of a potential-increasing agent or promoter and the resulting requirements for exhaust gas and wastewater treatment with high current yields at the same time Peroxodisulfate production.
- the electrolyte solution preferably contains from about 0.1 to about 3.5 mol of sulfuric acid per liter (l) of electrolyte solution, more preferably 1-3 mol of sulfuric acid per liter of electrolyte solution, and most preferably 2.2-2.8 mol of sulfuric acid per liter of electrolyte solution.
- an electrolyte with the following composition is particularly preferably used: 150 to 500 g of sulfate and 0.1 to 3.5 mol of sulfuric acid per liter of starting electrolyte per liter of electrolyte solution.
- the total solids content is preferably 0.5 g / l to 650 g / l, more preferably 100-500 g / l and most preferably 250-400 g / l.
- the promoter portion is 0 g / l.
- Figure 3 shows a possible embodiment of an electrolytic cell according to the present invention.
- FIG. 4 A cross section of this model is in Figure 4 shown schematically.
- the electrolyte reaches the distributor device (2a) through the feed pipe (1) and is fed from there to the electrolyte chamber (3) in a streamlined manner.
- the electrolyte space (3) is formed by the annular gap between the outer surface of the anode (4) and the inner surface of the cathode (5).
- the electrolysis product is collected by the distributor device (2b) and transferred into the drain pipe (6). Seals (7) close off the electrolyte space between the inlet or outlet pipe and the inner surface of the cathode.
- the distributor device (2) can be designed so that the distributor device simultaneously seals the electrolyte space.
- Figure 5 shows the individual components of the electrolytic cell according to the invention. The numbering is analogous Figure 4 . Further components for sealing the electrolytic cell and for assembly are in Figure 5 shown but not numbered. These components are known to the person skilled in the art and can be exchanged as required.
- FIG 6 is an enlarged view of the distribution device (2).
- the distributor device has a connection point (21) for an outlet or inlet pipe and a connection point (22) for the anode (4).
- the connection point for the anode is formed by a hollow cylinder that is flush with the anode tube or rod (4).
- Radial bores (23) are distributed over the circumference of the hollow cylinder of the distributor device.
- the electrolyte can be fed homogeneously into the electrolyte space through the radial bores (23) in the distributor device and can be effectively removed after passing through the electrolyte space.
- the distributor device preferably has 3, more preferably 4 and even more preferably 5 radial bores.
- a two-dimensional and on the other hand a three-dimensional cell consisting of a boron-doped diamond-coated niobium anode (diamond anode according to the invention) was used.
- the electrolyte was appropriately concentrated by circulating (see Figures 1 and 2 ).
- the current yield of a diamond-coated niobium anode is around 10% higher than with a cell with a conventional platinum-titanium anode and the addition of a potential-increasing agent and around 40% higher than with a cell with a conventional one, even without the addition of a potential-increasing agent Platinum-titanium anode without the addition of a potential-increasing agent.
- the voltage drop across a diamond-coated anode is about 0.9 volts higher than that of a comparable cell with a platinum-titanium anode. Furthermore, it was found that the current yield with a diamond electrode to be used according to the invention without the addition of a promoter only increases with an increasing total content of sodium peroxodisulfate in the electrolyte slowly decreases - under the experimental conditions, for example, electrolyte solutions with a sodium peroxodisulfate content of around 400 - 650 g / l can be obtained with a current yield of 65% or more.
- the working current density can be significantly reduced compared to platinum anodes with the same high production quantity, which means that fewer ohmic losses occur in the system and thus the cooling effort is reduced and the degree of freedom in the design of the electrolysis cells and the cathodes is increased.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Claims (13)
- Cellule d'électrolyse, comprenant les éléments constitutifs :(a) au moins une cathode en forme de tube,(b) au moins une anode en forme de barre ou de tube, qui comprend un support conducteur revêtu d'une couche de diamant conductrice,(c) au moins un tube d'amenée,(d) au moins un tube d'écoulement, et(e) au moins deux dispositifs de répartition, où les dispositifs de répartition présentent au moins un point de raccordement pour au moins un tube d'amenée ou d'écoulement et un point de raccordement pour l'anode et où le premier dispositif de répartition est conçu pour répartir un électrolyte du tube d'amenée dans un compartiment d'électrolyte et le second dispositif de répartition est conçu pour collecter l'électrolyte qui a réagi et pour l'évacuer par le tube d'écoulement,et où le compartiment d'électrolyte est formé sous forme d'une fente annulaire entre l'anode située à l'intérieur et la cathode située à l'extérieur.
- Cellule d'électrolyse selon la revendication 1, où la cellule d'électrolyse présente un compartiment d'électrolyte commun sans diaphragme.
- Cellule d'électrolyse selon la revendication 1 ou 2, où la distance entre la surface externe de l'anode et la surface interne de la cathode est entre 1 et 20 mm.
- Cellule d'électrolyse selon l'une des revendications 1-3, où le diamètre interne de la cathode est entre 10 et 400 mm.
- Cellule d'électrolyse selon l'une des revendications 1-4, où l'anode et la cathode ont chacune indépendamment l'une de l'autre une longueur entre 20 et 120 cm.
- Cellule d'électrolyse selon l'une des revendications 1-5, où le support est choisi dans le groupe consistant en le silicium, le germanium, le titane, le zirconium, le niobium, le tantale, le molybdène, le tungstène, les carbures de ces éléments, et/ou l'aluminium, ou des combinaisons des éléments.
- Cellule d'électrolyse selon l'une des revendications 1-6, où la couche de diamant est dopée avec au moins un élément de groupe principal ou de groupe secondaire trivalent ou au moins pentavalent, en particulier le bore et/ou le phosphore.
- Cellule d'électrolyse selon l'une des revendications 1-7, où la cathode est réalisée en plomb, en carbone, en étain, en platine, en nickel, en alliages de ces éléments, en zirconium et/ou en alliages du fer, en particulier en acier spécial résistant aux acides.
- Cellule d'électrolyse selon l'une des revendications 1-8, où les éléments constitutifs de la cellule d'électrolyse sont remplaçables individuellement.
- Dispositif d'électrolyse, comprenant au moins deux cellules d'électrolyse selon l'une des revendications 1-9, où l'électrolyte traverse les cellules d'électrolyse les unes après les autres et les cellules d'électrolyse sont branchées en parallèle électrochimiquement.
- Utilisation de la cellule d'électrolyse selon l'une des revendications 1-9 ou du dispositif d'électrolyse selon la revendication 10 pour l'oxydation d'un électrolyte.
- Utilisation selon la revendication 11, où la densité de courant est entre 50 et 1500 mA/cm2.
- Utilisation selon l'une des revendications 11 ou 12 pour la production de peroxodisulfate.
Priority Applications (2)
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PL13735335T PL2872673T3 (pl) | 2012-07-13 | 2013-07-12 | Niepodzielone ogniwo elektrolityczne i jego zastosowanie |
US14/407,205 US9540740B2 (en) | 2012-07-13 | 2013-07-12 | Undivided electrolytic cell and use thereof |
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Application Number | Priority Date | Filing Date | Title |
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PCT/EP2012/063783 WO2013007816A2 (fr) | 2011-07-14 | 2012-07-13 | Cellule électrolytique non divisée et son utilisation |
PCT/EP2013/064809 WO2014009536A1 (fr) | 2012-07-13 | 2013-07-12 | Cellule électrolytique dépourvue de séparateur et son utilisation |
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EP2872673B1 true EP2872673B1 (fr) | 2020-09-09 |
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EP (1) | EP2872673B1 (fr) |
KR (1) | KR20150034171A (fr) |
TW (1) | TW201406998A (fr) |
WO (1) | WO2014009536A1 (fr) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2346945C3 (de) | 1973-09-18 | 1982-05-19 | Peroxid-Chemie GmbH, 8023 Höllriegelskreuth | Verfahren zur direkten elektrolytischen Herstellung von Natriumperoxodisulfat |
US3984303A (en) * | 1975-07-02 | 1976-10-05 | Diamond Shamrock Corporation | Membrane electrolytic cell with concentric electrodes |
CA1090286A (fr) | 1976-12-23 | 1980-11-25 | Kenneth J. Radimer | Fabrication electrolytique du persulfate de sodium |
DE3938160A1 (de) | 1989-11-16 | 1991-05-23 | Peroxid Chemie Gmbh | Elektrolysezelle zur herstellung von peroxo- und perhalogenatverbindungen |
TW416997B (en) | 1998-03-30 | 2001-01-01 | Mitsubishi Gas Chemical Co | Process for producing persulfate |
DE19911746A1 (de) | 1999-03-16 | 2000-09-21 | Basf Ag | Diamantelektroden |
DE10019683A1 (de) | 2000-04-20 | 2001-10-25 | Degussa | Verfahren zur Herstellung von Alkalimetall- und Ammoniumperoxodisulfat |
DE20318754U1 (de) * | 2003-12-04 | 2004-02-19 | Schulze, Dirk | Elektrochemischer Ozonerzeuger |
DE102004027623A1 (de) * | 2004-06-05 | 2005-12-22 | Degussa Initiators Gmbh & Co. Kg | Verfahren zur Herstellung von Peroxodisulfaten in wässriger Lösung |
BRPI0905277B1 (pt) * | 2009-12-01 | 2019-11-26 | Univ Estadual Campinas Unicamp | célula eletroquímica cilíndrica com anodo de diamante dopado coaxial |
-
2013
- 2013-07-11 TW TW102124932A patent/TW201406998A/zh unknown
- 2013-07-12 KR KR1020157000758A patent/KR20150034171A/ko not_active Application Discontinuation
- 2013-07-12 WO PCT/EP2013/064809 patent/WO2014009536A1/fr active Application Filing
- 2013-07-12 EP EP13735335.5A patent/EP2872673B1/fr active Active
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KR20150034171A (ko) | 2015-04-02 |
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TW201406998A (zh) | 2014-02-16 |
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