WO2023274794A1 - Dreikammerelektrolysezelle zur herstellung von alkalimetallalkoholaten - Google Patents
Dreikammerelektrolysezelle zur herstellung von alkalimetallalkoholaten Download PDFInfo
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- WO2023274794A1 WO2023274794A1 PCT/EP2022/066937 EP2022066937W WO2023274794A1 WO 2023274794 A1 WO2023274794 A1 WO 2023274794A1 EP 2022066937 W EP2022066937 W EP 2022066937W WO 2023274794 A1 WO2023274794 A1 WO 2023274794A1
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- Prior art keywords
- chamber
- electrolytic cell
- solution
- stirring device
- mechanical stirring
- Prior art date
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- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- -1 alkali metal alkoxides Chemical class 0.000 title claims description 33
- 239000000243 solution Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 43
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 42
- 238000009792 diffusion process Methods 0.000 claims abstract description 39
- 230000004888 barrier function Effects 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910004283 SiO 4 Inorganic materials 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 150000001450 anions Chemical class 0.000 abstract description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 230000005484 gravity Effects 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 241000047703 Nonion Species 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000010327 methods by industry Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
- C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
-
- 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
- C25B9/13—Single electrolytic cells with circulation of an electrolyte
-
- 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
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
Definitions
- the present invention relates to an electrolytic cell which has three chambers, the middle chamber being separated from the cathode chamber by a solid electrolyte which is permeable to cations, for example NaSICON, and from the anode chamber by a diffusion barrier.
- the invention is characterized in that the middle chamber comprises a mechanical stirring device.
- the electrolytic cell according to the invention solves the problem that a concentration gradient forms in the middle chamber of the electrolytic cell during electrolysis, which leads to locally reduced pH values and thus to damage to the solid electrolyte.
- the mechanical stirring device can be used to stir the electrolyte solution in the middle chamber during electrolysis, which prevents the formation of a pH gradient.
- the present invention relates to a method for producing an alkali metal alkoxide solution in the electrolytic cell according to the invention.
- Electrolytic cell reflected in the anode chamber is the solution of an alkali salt, such as common salt or NaOH
- an alkali salt such as common salt or NaOH
- the cathode chamber is the alcohol in question or a low-concentration alcoholic solution of the alkali metal alkoxide in question, such as sodium methoxide or sodium ethoxide.
- the cathode compartment and the anode compartment are separated by a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
- the charge is equalized by the alkali metal ions migrating from the middle chamber into the cathode chamber via the ceramic that is selective for them.
- the charge equalization between the middle chamber and the anode chamber takes place through the migration of cations when using cation exchange membranes or the migration of anions when using anion exchange membranes or through the migration of both types of ions when using non-specific diffusion barriers. This increases the concentration of the alkali alcoholate in the cathode chamber and the concentration of the sodium ions in the anolyte decreases.
- NaSICON solid electrolytes are also used in the electrochemical production of other compounds: WO 2014/008410 A1 describes an electrolytic process for the production of elemental titanium or rare earths. This process is based on the fact that titanium chloride is formed from T1O2 and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally electrolytically converted to elementary titanium and sodium alcoholate.
- WO 2007/082092 A2 and WO 2009/059315 A1 describe processes for the production of biodiesel in which triglycerides are first converted into the corresponding alkali metal triglycerides with the aid of alcoholates electrolytically produced via NaSICON and in a second step with electrolytically produced protons to form glycerol and the respective alkali metal hydroxide be implemented.
- WO 2012/048032 A2 and US 2010/0044242 A1 describe, for example, electrochemical methods for producing sodium hypochlorite and similar chlorine compounds in such a three-chamber cell.
- the cathode chamber and the middle chamber of the cell are separated by a cation-permeable solid electrolyte such as NaSICON.
- the middle chamber is supplied with solution from the cathode chamber, for example.
- US 2010/0044242 A1 also describes in Figure 6 that solution from the middle chamber can be mixed with solution from the anode chamber outside the chamber in order to obtain sodium hypochlorite.
- US Pat. No. 5,389,211 A describes a process for purifying alkoxide solutions in which a three-chamber cell is used, in which the chambers are separated from one another by cation-selective solid electrolytes or non-ionic partitions.
- the middle chamber is used as a buffer chamber to prevent the cleaned Alkoxide or hydroxide solution from the cathode compartment mixes with the contaminated solution from the anode compartment.
- DE 4233 191 A1 describes the electrolytic production of alkoxides from salts and alkoxides in multi-chamber cells and stacks of several cells.
- WO 2008/076327 A1 describes a process for preparing alkali metal alkoxides.
- a three-chamber cell is used, the middle chamber of which is filled with alkali metal alkoxide (see, for example, paragraphs [0008] and [0067] of WO 2008/076327 A1).
- WO 2009/073062 A1 describes a process for preparing alkali metal alkoxides.
- this arrangement has the disadvantage that the alkali metal alkoxide solution is the desired product, but this is consumed as a buffer solution and is continuously contaminated.
- the central chamber is separated from the anode chamber by a diffusion barrier and from the cathode chamber by an ion-conducting ceramic.
- ion-conducting ceramic During the electrolysis, this inevitably leads to the formation of pH gradients and dead volumes. This can damage the ion-conducting ceramic and consequently increase the voltage requirement of the electrolysis and/or lead to breakage of the ceramic.
- the object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide and an electrolysis chamber which is particularly suitable for such a process. These should not have the aforementioned disadvantages and should in particular ensure improved protection of the solid electrolyte against the formation of the pH gradient and more economical use of the educts compared to the prior art. 2. Summary of the Invention
- the electrolytic cell E ⁇ 100> comprises at least one anode chamber K ⁇ 101>, at least one cathode chamber K ⁇ 102> and at least one intermediate chamber K ⁇ 103>, where K ⁇ 101> an anodic electrode E A ⁇ 104> and an outlet A K ⁇ ⁇ 106>, where K K ⁇ 102> comprises a cathodic electrode E K ⁇ 105>, an inlet Z KK ⁇ 107> and an outlet AKK ⁇ 109>, where K ⁇ 103> a Inlet Z K M ⁇ 108> is separated from K A ⁇ 101> by a diffusion barrier D ⁇ 110> and separated from K K ⁇ 102> by an alkali cation-conducting solid electrolyte F K ⁇ 111>, where K ⁇ 103> and K A ⁇ 101> are connected to each other by a connection V A ⁇ 112>, through which liquid can be passed from K ⁇ 103> to K A ⁇ 101>, and is characterized in that the central chamber K
- the present invention relates to a method for preparing a solution Li ⁇ 115> of an alkali metal alkoxide XOR in the alcohol ROH in an electrolytic cell E ⁇ 100> according to the first aspect of the invention, the method comprising the following steps (a) , (b) and (c) includes:
- Figure 1 shows a preferred embodiment of an electrolytic cell ⁇ 100> according to the invention and of the method according to the invention.
- the three-chamber cell E ⁇ 100> comprises a cathode chamber K K ⁇ 102>, an anode chamber K ⁇ 101> and a middle chamber K ⁇ 103> lying in between.
- the cathode chamber K K ⁇ 102> comprises a cathodic electrode E K ⁇ 105>, an inlet ZKK ⁇ 107> and an outlet AKK ⁇ 109>.
- the anode chamber K ⁇ 101> comprises an anodic electrode E A ⁇ 104> and an outlet AK ⁇ ⁇ 106> and is connected to the middle chamber K ⁇ 103> via the connection V A ⁇ 112>.
- the middle chamber K ⁇ 103> includes an inlet Z K M ⁇ 108>.
- the three chambers are delimited by an outer wall ⁇ 117> of the three-chamber cell E ⁇ 100>.
- the cathode chamber K K ⁇ 102> is also separated from the middle chamber K ⁇ 103> by a NaSICON solid electrolyte F K ⁇ 111> that is selectively permeable for sodium ions.
- the middle chamber K ⁇ 103> is in turn separated from the anode chamber K A ⁇ 101> by a diffusion barrier D ⁇ 110>.
- the NaSICON solid electrolyte F K ⁇ 111> and the diffusion barrier D ⁇ 110> extend over the entire depth and height of the three-chamber cell E ⁇ 100>.
- the diffusion barrier D ⁇ 110> is made of glass.
- connection V A ⁇ 112> is formed outside the electrolytic cell E ⁇ 100>, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic.
- liquid can be conducted from the middle chamber K ⁇ 103> into the anode chamber K A ⁇ 101> outside the outer wall W A ⁇ 117> of the three-chamber cell E ⁇ 100>.
- connection V A ⁇ 112> connects an outlet A K M ⁇ 118>, which breaks through the outer wall W A ⁇ 117> of the electrolytic cell E ⁇ 100> at the bottom of the central chamber K ⁇ 103>, with an inlet Z KA ⁇ 119>, which breaks through the outer wall W A ⁇ 117> of the electrolytic cell E ⁇ 100> at the bottom of the anode chamber K A ⁇ 101>.
- An aqueous solution of sodium chloride L 3 ⁇ 114> with a pH of 10.5 is introduced via the inlet Z K M ⁇ 108> in the same direction as gravity into the middle chamber K ⁇ 103>.
- connection V AM ⁇ 112> which is formed between an outlet A K M ⁇ 118> of the middle chamber K ⁇ 103> and an inlet Z KA ⁇ 119> of the anode chamber K A ⁇ 101>, forms the middle chamber K ⁇ 103> connected to the anode chamber K A ⁇ 101 >.
- Sodium chloride solution L 3 ⁇ 114> is conducted through this connection V A M ⁇ 112> from the middle chamber K ⁇ 103> into the anode chamber K A ⁇ 101>.
- a solution of sodium methoxide in methanol L 2 ⁇ 113> is fed into the cathode chamber K K ⁇ 102> via the inlet ZKK ⁇ 107>.
- a mechanical stirring device ⁇ 120> in the form of a propeller stirrer ⁇ 121>, which is operated by an electric motor ⁇ 122>, the propeller stirrer being connected to the electric motor via a transmission element ⁇ 124> .
- the propeller stirrer ⁇ 121> hangs freely in the middle chamber K ⁇ 103>, but can also be attached to the inside of the outer wall W A ⁇ 117>.
- the transmission element ⁇ 124> extends through an opening ⁇ 125> in the outer wall of the middle chamber K ⁇ 103> into the electrolytic cell E ⁇ 100>.
- the aqueous solution L 3 ⁇ 114> supplied through the inlet Z KM ⁇ 108> is mixed by the operation of the propeller stirrer ⁇ 121>, which leads to eddies and turbulence.
- These turbulences in the solution L 3 ⁇ 114> prevent a pH gradient building up in the central chamber K ⁇ 103> as the electrolysis progresses and prevent the formation of a low pH value in the solution immediately adjacent to the NaSICON solid electrolyte ⁇ 111> . This further increases the durability of the NaSICON solid electrolyte ⁇ 111>.
- FIG. 2 shows a further embodiment of the electrolytic cell according to the invention and of the method according to the invention, which corresponds to that shown in FIG.
- the mechanical stirring device ⁇ 120> comprises a magnetic stirring bar ⁇ 123-1> instead of the propeller stirrer ⁇ 121> described in Figure 1, which is operated with a magnetic stirring drive ⁇ 123-2> located outside the central chamber K ⁇ 103> can.
- the aqueous solution L 3 ⁇ 114> supplied through the inlet ZKM ⁇ 108> is swirled by this mechanical stirring device ⁇ 120>.
- Electrolysis cell E The first aspect of the invention relates to an electrolysis cell E ⁇ 100>.
- the electrolytic cell E ⁇ 100> according to the first aspect of the invention comprises at least one anode chamber K ⁇ 101>, at least one cathode chamber K ⁇ 102> and at least one intermediate chamber K ⁇ 103>.
- This also includes electrolytic cells E ⁇ 100>, which have more than one anode chamber KA ⁇ 101> and/or cathode chamber KK ⁇ 102> and/or middle chamber K - ⁇ 103>.
- Such electrolytic cells, in which these chambers are joined together in a modular manner, are described, for example, in DD 258 143 A3 and US 2006/0226022 A1.
- the anode chamber K A ⁇ 101> includes an anodic electrode E A ⁇ 104>.
- Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the second aspect of the invention can be used as such an anodic electrode E A ⁇ 104>. Such are described in particular in WO 2014/008410 A1, paragraph [024] or DE 10360758 A1, paragraph [031].
- This electrode E A ⁇ 104> can consist of one layer or of several planar layers parallel to one another, each of which can be perforated or expanded.
- the anodic electrode E A ⁇ 104> includes in particular a material selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt,
- a carrier such as titanium or Kovar ® (an iron/nickel/cobalt alloy in which the individual proportions are preferably as follows: 54% by mass iron, 29% by mass nickel, 17% by mass cobalt) is supported.
- Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride.
- the anodic electrode E A ⁇ 104> preferably comprises a titanium anode (RuÜ2+ I rÜ2 /Ti) coated with ruthenium oxide/iridium oxide.
- the cathode chamber K K ⁇ 102> includes a cathodic electrode E K ⁇ 105>. Any electrode familiar to a person skilled in the art that is stable under the conditions can be used as such a cathodic electrode E K ⁇ 105>. Such are described in particular in WO 2014/008410 A1, paragraph [025] or DE 10360758 A1, paragraph [030].
- This electrode E K ⁇ 105> can be selected from the group consisting of mesh wool, three-dimensional matrix structure or “balls”.
- the cathodic electrode E K ⁇ 105> comprises in particular a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium. E K ⁇ 105> preferably comprises nickel.
- the at least one middle chamber K ⁇ 103> is located between the anode chamber K ⁇ 101> and the cathode chamber K ⁇ 102>.
- the electrolytic cell E ⁇ 100> usually has an outer wall W ⁇ 117>.
- the outer wall W ⁇ 117> is in particular made of a material selected from the group consisting of steel, preferably rubberized steel, plastic, in particular Telene® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride) is selected.
- W ⁇ 117> can be perforated in particular for inlets and outlets.
- the at least one anode chamber K A ⁇ 101>, the at least one cathode chamber K K ⁇ 102> and the at least one middle chamber K ⁇ 103> lying in between are then located within W A ⁇ 117>.
- K ⁇ 103> is separated from K A ⁇ 101> by a diffusion barrier D ⁇ 110> and separated from K K ⁇ 102> by an alkali cation-conducting solid electrolyte F K ⁇ 111>.
- Any material which is stable under the conditions of the method according to the second aspect of the invention and which prevents the transfer of protons from the liquid in the anode chamber K A ⁇ 101> into the middle chamber K ⁇ can be used for the diffusion barrier D ⁇ 110>103> prevented or slowed down.
- a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D ⁇ 110>.
- the diffusion barrier D ⁇ 110> is preferably a non-ion-specific partition.
- the material of the non-ion-specific partition wall is in particular selected from the group consisting of fabric, in particular textile fabric or metal fabric, glass, in particular sintered glass or glass frits, ceramic, in particular ceramic frits, membrane diaphragms, and is selected particularly preferably glass.
- the diffusion barrier D ⁇ 110> is a “membrane permeable to specific ions”
- membranes are meant that favor the diffusion through them of ions of a certain type of charge compared to oppositely charged ions. More preferably, specific ion permeable membranes also favor the diffusion of certain ions having one charge type through them over other ions of the same charge type.
- the diffusion barrier D ⁇ 110> is a “membrane permeable to specific ions”
- the diffusion barrier D ⁇ 110> is in particular an anion-conducting membrane or a cation-conducting membrane.
- anion-conducting membranes are those which selectively conduct anions, preferably selectively specific anions. In other words, they favor the diffusion of anions through them over that of cations, especially protons, more preferably they additionally favor the diffusion of certain anions through them over the diffusion of other anions through them.
- cation-conducting membranes are those which selectively conduct cations, preferably selectively specific cations. In other words, they favor the diffusion of cations through them over that of anions, more preferably they additionally favor the diffusion of certain cations through them over the diffusion of other cations through them, much more preferably cations where there is are not protons, more preferably sodium cations, over protons.
- “Favour the diffusion of certain ions X compared to the diffusion of other ions Y” means in particular that the diffusion coefficient (unit m 2 /s) of the ion type X at a given temperature for the membrane in question is higher by a factor of 10, preferably 100, preferably 1000 as the diffusion coefficient of the ionic species Y for the membrane in question.
- the diffusion barrier D ⁇ 110> is a "membrane that is permeable to specific ions"
- it is preferably an anion-conducting membrane, because this is particularly good at preventing the diffusion of protons from the anode chamber K ⁇ 101 > into the middle chamber K ⁇ 103 >.
- a membrane which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
- Such membranes are known to those skilled in the art and can be used by them.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- a membrane selective for halides is preferably used as the anion-conducting membrane.
- Anion conducting membranes are available, for example, from M.A. Hickner, A.M. Herring, E.B. Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51 1727-1735, by C.G. Arges,
- the diffusion barrier D ⁇ 110> is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S. Even more preferably, the diffusion barrier D ⁇ 110> is an alkali cation-conducting membrane, even more preferably a potassium and/or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.
- Cation-conducting membranes are described, for example, on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003).
- Organic polymers which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are therefore even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -S0 3 - , -COO-, -PO3 2 , -PO2H-, preferably -SO3- (described in DE 102010 062 804 A1, US Pat. No. 4,831, 146).
- This can be, for example, a sulfonated polyperfluoroethylene (Nafion ® with CAS number:
- a cation-conducting membrane is used as the diffusion barrier D ⁇ 110>, this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula PNAFION, where n and m are independently an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , more preferably an integer from 10 2 to 10 4 .
- PNAFION a polymer functionalized with sulfonic acid groups
- any solid electrolyte which can transport cations, in particular alkali cations, more preferably sodium cations, from the central chamber K ⁇ 103> into the cathode chamber K K ⁇ 102> can be used as the alkali cation-conducting solid electrolyte F K ⁇ 111>.
- Such solid electrolytes are known to the person skilled in the art and for example in DE 102015 013 155 A1, in WO 2012/048032 A2, paragraphs [0035], [0039], [0040], in US 2010/0044242 A1, paragraphs [0040], [0041], in DE 10360758 A1, paragraphs [014] to [025]. They are sold commercially under the names NaSICON, LiSICON, KSICON.
- a sodium ion conductive solid electrolyte F K ⁇ 111> is preferred, which more preferably has a NaSICON structure.
- NaSICON structures that can be used according to the invention are also described, for example, by N. Anantharamulu, K. Koteswara Rao, G. Rambabu, B. Vijaya Kumar, Velchuri Radha,
- NaSICON preferably has a structure of the formula M I 1+2w+x-y+z M II M III x Zr lv 2- -xy M v y (SiO 4 )z M' is selected from Na + , Li + , preferably Na + .
- M" is a divalent metal cation preferably selected from Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 2+ , Ni 2+ , more preferably selected from Co 2+ , Ni 2+ .
- M m is a trivalent metal cation, preferably selected from Al 3+ , Ga 3+ , Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , Lu 3+ , Fe 3+ , Cr 3+ , more preferably selected from Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , particularly preferably selected from Sc 3+ , Y 3+ , La 3+ .
- M v is a pentavalent metal cation, preferably selected from V 5+ , Nb 5+ , Ta 5+ .
- w, x, y, z are real numbers, where 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2, 0 ⁇ w ⁇ 2, 0 ⁇ z ⁇ 3, and where w, x, y, z are so chosen become that 1 + 2w + x - y + z > 0 and 2 - w - x - y > 0.
- the cathode chamber K K ⁇ 102> also comprises an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>, which allows liquid, such as the solution L 2 ⁇ 113>, to flow into the cathode chamber K K ⁇ 102>. to add and liquid contained therein, such as the solution Li ⁇ 115> to remove.
- the inlet ZKK ⁇ 107> and the outlet AKK ⁇ 109> are attached to the cathode chamber K K ⁇ 102> in such a way that the liquid makes contact with the cathodic electrode E K ⁇ 105> as it flows through the cathode chamber K K ⁇ 102>.
- This is the prerequisite for the solution Li ⁇ 115> being obtained when the method according to the invention is carried out according to the second aspect of the invention at the outlet AKK ⁇ 109> if the solution L 2 ⁇ 113> of an alkali metal alcoholate XOR in the alcohol ROH is replaced by K K ⁇ 102> is conducted.
- the anode chamber K ⁇ 101> also includes an outlet AKA ⁇ 106>, which makes it possible to remove liquid located in the anode chamber K A ⁇ 101>, for example the aqueous solution L 4 ⁇ 116>.
- the central chamber K ⁇ 103> includes an inlet Z K M ⁇ 108>, while K A ⁇ 101 > and K ⁇ 103> are connected to one another by a connection V AM ⁇ 112>, through which liquid from K ⁇ 103> flows into K A ⁇ 101> can be routed.
- a solution L 3 ⁇ 114> can be added to K ⁇ 103> via the inlet Z K M ⁇ 108> and this can be conducted through K ⁇ 103>, then via V A ⁇ 112> into the anode chamber K A ⁇ 101>, and finally through the anode chamber K A ⁇ 101>.
- V A ⁇ 112> and the drain A KA ⁇ 106> are attached to the anode chamber K A ⁇ 101> in such a way that the solution L 3 ⁇ 114> when flowing through the anode chamber K A ⁇ 101> the anodic electrode E A ⁇ 104 > contacted.
- the inlets ZKK ⁇ 107>, ZKM ⁇ 108>, ZK A ⁇ 119> and outlets AKK ⁇ 109>, AK A ⁇ 106>, AKM ⁇ 118> can be attached to the electrolytic cell E ⁇ 100> by methods known to those skilled in the art.
- connection V A M ⁇ 112> can be formed inside the electrolytic cell E ⁇ 100> and/or outside, preferably inside, the electrolytic cell E ⁇ 100>.
- connection V A M ⁇ 112> is formed within the electrolytic cell E ⁇ 100>, it is preferably formed by at least one perforation in the diffusion barrier D ⁇ 110>.
- connection V A M ⁇ 112> is formed outside the electrolytic cell E ⁇ 100>, it is preferably formed by a connection of K ⁇ 103> and K A ⁇ 101> running outside the electrolytic cell E ⁇ 100>, in particular by the fact that in the middle chamber K ⁇ 103> an outlet AKM ⁇ 118> through the outer wall WA ⁇ 117>, preferably at the bottom of the middle chamber K ⁇ 103>, with the inlet ZKM ⁇ 108> even more preferably at the top of the middle chamber K ⁇ 103> , is formed, and in the anode chamber K A ⁇ 101> an inlet ZKA ⁇ 119> through the outer wall W ⁇ 117>, preferably at the bottom of the anode chamber K ⁇ 101>, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
- the outlet AK ⁇ ⁇ 106> is then even more preferably at the top of the anode chamber K A ⁇ 101>.
- Outflow AKM ⁇ 118> on the bottom of the middle chamber K ⁇ 103> means that the outflow AKM ⁇ 118> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> rectifies the middle chamber K ⁇ 103> leaves with gravity.
- Inlet ZK ⁇ ⁇ 119> at the bottom of the anode chamber K A ⁇ 101 > means that the inlet ZK ⁇ ⁇ 119> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> flows into the anode chamber K A ⁇ 101 > occurs against gravity.
- Inlet ZKM ⁇ 108> on the top of the middle chamber K ⁇ 103> means that the inlet ZKM ⁇ 108> SO is attached to the electrolytic cell E ⁇ 100>, that the solution L 3 ⁇ 114> in the middle chamber K ⁇ 103 > occurs in the same direction as gravity.
- Outflow AK ⁇ ⁇ 106> on the top of the anode chamber K A ⁇ 101 > means that the outflow A KA ⁇ 106> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 4 ⁇ 116> fills the anode chamber K A ⁇ 101> leaves against gravity.
- This embodiment is particularly advantageous and therefore preferred if the outlet AKM ⁇ 118> through the outer wall WA ⁇ 117> on the bottom of the middle chamber K ⁇ 103>, and the inlet ZK ⁇ ⁇ 119> through the outer wall WA ⁇ 117> at the bottom of the anode chamber K A ⁇ 101 >.
- This arrangement makes it particularly easy to discharge gases with L 4 ⁇ 116> formed in the anode chamber K A from the anode chamber K A ⁇ 101> in order to then separate them further.
- connection V AM ⁇ 112> is formed outside the electrolytic cell E ⁇ 100>, in particular ZKM ⁇ 108> and AKM ⁇ 118> are arranged on opposite sides of the outer wall WA ⁇ 117> of the central chamber K ⁇ 103> (i.e. ZKM ⁇ 108> at the bottom and AKM ⁇ 118> at the top of the electrolytic cell E ⁇ 100> or vice versa) and Z KA ⁇ 119> and AK ⁇ ⁇ 106> on opposite sides of the outer wall W A ⁇ 117> of the anode chamber K A ⁇ 101 > Arranged (i.e.
- ZK ⁇ ⁇ 119> on the bottom and AK ⁇ ⁇ 106> on the top of the electrolytic cell E ⁇ 100> or vice versa Due to this geometry, L 3 ⁇ 114> must flow through the two chambers K ⁇ 103> and KA ⁇ 101>. In this case, Z KA ⁇ 119> and ZKM ⁇ 108> can be formed on the same side of electrolytic cell E ⁇ 100>, with AKM ⁇ 118> and AK ⁇ ⁇ 106> then automatically also being formed on the same side of electrolytic cell E ⁇ 100>.
- ZK ⁇ ⁇ 119> and ZKM ⁇ 108> can be formed on opposite sides of the electrolytic cell E ⁇ 100>, in which case A KM ⁇ 118> and A KA ⁇ 106> are automatically also formed on opposite sides of the electrolytic cell E ⁇ 100>.
- connection VAM ⁇ 112> is formed inside the electrolytic cell E ⁇ 100>, this can be ensured in that one side ("side A") of the electrolytic cell E ⁇ 100>, which is the top or the bottom of the electrolytic cell E ⁇ 100>, preferably as shown in Figure 2 is the upper side, includes the inlet ZKM ⁇ 108> and the outlet AKA ⁇ 106> and the diffusion barrier D ⁇ 110> starting from this side ("side A") extends into the E ⁇ 100> electrolytic cell but not all the way to the opposite side (“B side”) of the E ⁇ 100> electrolytic cell from side A, which is then the bottom or top of the E ⁇ electrolytic cell 100> is sufficient and is 50% or more of the height of the three-chamber cell E ⁇ 100>, more preferably 60% to 99% of the height of the three-chamber cell E ⁇ 100>, even more preferably 70% to 95% of the height of the three-chamber cell E ⁇ 100> , more preferably 80% to 90% of the height of the
- top side of the electrolytic cell E is the side of the electrolytic cell E through which a solution (eg L 4 ⁇ 116> at AKA ⁇ 106> and Li ⁇ 115> at AKK ⁇ 109> in Figures 1 and 2) flows out against the force of gravity of the electrolytic cell E or the side of the electrolytic cell E through which a solution (e.g. L 3 ⁇ 114> at Z KM ⁇ 108> in Figures 1 and 2) is fed to the electrolytic cell E in the same direction as gravity.
- a solution e.g L 4 ⁇ 116> at AKA ⁇ 106> and Li ⁇ 115> at AKK ⁇ 109> in Figures 1 and 2
- the middle chamber K comprises a mechanical stirring device ⁇ 120>.
- the mechanical stirring device ⁇ 120> is in the solid state of aggregation. Any stirring device known to those skilled in the art that is sufficiently inert to the electrolysis conditions is suitable as such a mechanical stirring device.
- the mechanical stirring device ⁇ 120> comprises at least one material selected from rubber; Plastic chosen in particular from polystyrene, polypropylene, PVC, PVC-C; Glass; Porcelain; Metal.
- the metal is in particular a metal or an alloy of several metals selected from titanium, iron, molybdenum, chromium, nickel, platinum, gold, silver, preferably an alloy comprising at least two metals selected from titanium, iron, molybdenum and chromium , nickel, platinum, gold, silver, more preferably a steel alloy comprising, in addition to iron, at least one other metal selected from titanium, molybdenum, chromium, nickel, platinum, gold, silver, and most preferably it is stainless steel.
- the mechanical stirring device ⁇ 120> comprises magnetic material so that it can be operated with a magnetic stirrer.
- the mechanical stirring device ⁇ 120> is selected in particular from a propeller stirrer, inclined blade stirrer, disc stirrer, swashplate stirrer, hollow blade stirrer, impeller stirrer, cross bar stirrer, anchor stirrer, blade stirrer, grid stirrer, helical stirrer, toothed disc stirrer, residue stirrer, preferably a propeller stirrer.
- the mechanical stirring device ⁇ 120> is typically powered by a motor, which is preferably an electric motor external to the electrolytic cell E ⁇ 100>.
- a motor which is preferably an electric motor external to the electrolytic cell E ⁇ 100>.
- this can be a motor ⁇ 122>, which is connected to the propeller stirrer ⁇ 121> via a transmission element ⁇ 124>, the transmission element ⁇ 124> passing through an opening ⁇ 125> in the outer wall of the central chamber K ⁇ 103> into the Electrolytic cell E ⁇ 100> as illustrated in Figure 1.
- the propeller stirrer can also be magnetic, so that it is a magnetic stirrer bar ⁇ 123-1> (another word "magnetic stirrer bar”), which is operated by a magnetic stirrer drive ⁇ 123-2> located outside the central chamber K ⁇ 103>, such as it is illustrated in Figure 2.
- the mechanical stirring device ⁇ 120> can hang loosely in the center chamber K ⁇ 103> as shown in Figure 1.
- the mechanical stirring device ⁇ 120> can also be attached, for example to the solid electrolyte F K ⁇ 111>, to the diffusion barrier D ⁇ 110> or to the outer wall ⁇ 117> delimiting the inside of the central chamber K ⁇ 103>.
- the attachment can be done by methods known to those skilled in the art, for example by screwing, clamping, gluing (plastic adhesive, PVC adhesive).
- the mechanical stirring device ⁇ 120> comprises a propeller which is aligned parallel to the alkali cation-conducting solid electrolyte F K ⁇ 111>.
- the mechanical stirring device ⁇ 120> makes a proportion z of 1 to 99%, more preferably 2 to 50%, more preferably 3 to 40%, more preferably 4 to 30% %, more preferably 5 to 20%, most preferably 6 to 10% of the volume comprised by the middle chamber K.
- V 0 is the maximum volume of liquid, for example the electrolyte L 3 ⁇ 114>, which the middle chamber K ⁇ 103> can hold if it does not include a mechanical stirring device ⁇ 120>.
- V is the maximum volume of liquid, eg the electrolyte L 3 ⁇ 114>, which the central chamber K ⁇ 103> can hold if it includes the mechanical stirring device ⁇ 120>.
- the mechanical stirring device ⁇ 120> in the middle chamber K ⁇ 103> leads to turbulence and turbulence in the electrolyte L 3 ⁇ 114> flowing through the middle chamber K ⁇ 103> during the method according to the invention. This slows down or completely prevents the build-up of a pH gradient during the electrolysis, which protects the acid-sensitive solid electrolyte F K ⁇ 111> and thus enables the electrolysis to run longer or extends the service life of the electrolysis cell E ⁇ 100>.
- the mechanical stirring device ⁇ 120> is placed in the middle chamber K ⁇ 103> in such a way that it allows the flow of the electrolyte L 3 ⁇ 114> through the middle chamber K ⁇ 103> and the anode chamber K ⁇ 101> in allows sufficient extent or not completely blocked.
- the mechanical stirring device ⁇ 120> interrupts the direct path in the middle chamber K between inlet ZKM ⁇ 108> and connection V A M ⁇ 112>.
- a thread is fed through the opening through which the inlet Z KM ⁇ 108> opens into the middle chamber K, and out of the opening through which the connection V A M ⁇ 112> in the middle chamber K opens.
- the thread is so long that its ends lie outside the central chamber K.
- the thread is selected in particular from sewing thread (e.g. from the Heilrmann company), fishing line, twine.
- a fishing line with a diameter of 0.2 mm such as that sold by the companies Hemingway or Nexos, is most preferably used for the thread test.
- the method according to the second aspect of the invention is one for preparing a solution Li ⁇ 115> of an alkali metal alkoxide XOR in the alcohol ROH in an electrolytic cell E ⁇ 100> according to the first aspect of the invention.
- the method according to the second aspect of the invention comprises the following steps (a), (b) and (c) occurring simultaneously.
- step (a) a solution L 2 ⁇ 113> comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through K K ⁇ 102>.
- X is an alkali metal cation and R is an alkyl group of 1 to 4 carbon atoms.
- R is preferably selected from the group consisting of n-propyl, /so-propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.
- the solution L 2 ⁇ 113> is preferably free of water.
- “Free of water” means according to the invention that the weight of the water in the solution L 2 ⁇ 113> based on the weight of the alcohol ROH in the solution L 2 ⁇ 113> (mass ratio) ⁇ 1:10, more preferably ⁇ 1:20, more preferably ⁇ 1:100, more preferably ⁇ 0.5:100.
- the mass fraction of XOR in the solution L 2 ⁇ 113> is in particular >0 to 30% by weight, preferably 5 to 20% by weight, more preferably at 10 to 20% by weight, even more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
- the solution L 2 ⁇ 113> comprises XOR
- the mass ratio of XOR to alcohol ROH is still in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20 more preferably in the range 1:12 to 1:8, even more preferably at 1:10.
- step (b) a neutral or alkaline aqueous solution L 3 ⁇ 114> of a salt S comprising X as a cation is passed through K ⁇ 103>, then over V AM ⁇ 112>, then through K ⁇ 101>, while the mechanical Stirring device ⁇ 120> stirs the solution L 3 ⁇ 114> in K ⁇ 103>.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- the pH of the aqueous solution L 3 ⁇ 114> is >7.0, preferably in the range from 7 to 12, more preferably in the range from 8 to 11, even more preferably from 10 to 11, most preferably at 10.5.
- the mass fraction of the salt S in the solution L 3 ⁇ 113> is preferably in the range >0 to 20% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 10 to 20% by weight, most preferably at 20% by weight, based on the total solution L 3 ⁇ 113>.
- step (c) a voltage is then applied between E ⁇ 104> and E K ⁇ 105>.
- the charge source is known to those skilled in the art and is typically a Rectifier that converts alternating current into direct current and can generate certain voltages via voltage converters.
- This can be determined by a person skilled in the art by default.
- the area of the solid electrolyte that contacts the anolyte located in the middle chamber K ⁇ 103> is in particular 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , even more preferably 2.83 cm 2 .
- step (c) of the method according to the second aspect of the invention is carried out when both chambers K ⁇ 103> and K ⁇ 101> are at least partially loaded with L 3 ⁇ 114> and K K ⁇ 102> is at least partially loaded with L 2 ⁇ 113>.
- step (c) charge transport takes place between EA ⁇ 104> and EK ⁇ 105> implies that KK ⁇ 102>, K ⁇ 103> and KA ⁇ 101> simultaneously with L 2 ⁇ 113 > or
- L 3 ⁇ 114> are charged in such a way that they cover the electrodes EA ⁇ 104> and EK ⁇ 105> to such an extent that the current circuit is closed.
- this desired effect can be further intensified by varying the stirring speed of the mechanical stirring device ⁇ 120> while step (b) is being carried out, as a result of which further turbulence can be generated which promotes the formation of a pH disturb gradients.
- the method according to the second aspect of the invention is carried out continuously, ie step (a) and step (b) are carried out continuously and voltage is applied in accordance with step (c).
- the solution Li ⁇ 115> is obtained at outlet A KK ⁇ 109>, the concentration of XOR in Li ⁇ 115> being higher than in L 2 ⁇ 113>.
- the concentration of XOR in Li ⁇ 115> is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1 8 fold, still more preferably 1.077 to 1 4 fold. more preferably 1077 to 108 times higher than in L 2 ⁇ 113>, most preferably 1077 times higher than in L 2 ⁇ 113>, more preferably the mass fraction of XOR in Li ⁇ 115> and in L 2 ⁇ 113> is in the range of 10 to 20% by weight, more preferably 13 to 14% by weight.
- An aqueous solution L 4 ⁇ 116> of S is obtained at outlet AK A ⁇ 106>, the concentration of S in L 4 ⁇ 116> being lower than in L 3 ⁇ 114>.
- the concentration of the cation X in the aqueous solution L 3 ⁇ 114> is preferably in the range of 3.5 to 5 mol/l, more preferably 4 mol/l.
- the concentration of the cation X in the aqueous solution L 4 ⁇ 116> is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 ⁇ 114> used in each case.
- the method according to the second aspect of the invention is carried out at a temperature of 20°C to 70°C, preferably 35°C to 65°C, more preferably 35°C to 60°C, even more preferably 35°C to 50°C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
- hydrogen is typically produced in the cathode chamber K K ⁇ 102>, which can be removed from the cell via the outlet AKK ⁇ 109> together with the solution Li ⁇ 115>.
- the mixture of hydrogen and solution Li ⁇ 115> can then be separated by methods known to those skilled in the art.
- the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can form, which can be removed from the cell via the outlet A KK ⁇ 106> together with the solution L 4 ⁇ 116>.
- oxygen and/or carbon dioxide can also be formed, which can also be removed.
- the mixture of chlorine, oxygen and/or CO2 and solution L 4 ⁇ 116> can then be separated by methods known to those skilled in the art.
- the gases chlorine, oxygen and/or CO 2 have been separated from the solution L 4 ⁇ 116>, these can be separated from one another by methods known to those skilled in the art.
- the method according to the invention is therefore more efficient than the procedure described in WO 2008/076327 A1, in which the product solution is used for the middle chamber, which reduces the overall turnover.
- the acid-labile solid electrolyte is stabilized by preventing the formation of a pH gradient due to the mechanical stirring device ⁇ 120>.
- NM Sodium methylate
- the electrolytic cell consisted of three chambers, which corresponded to those shown in Figure 1, except that the electrolytic cell did not have a mechanical stirring device ⁇ 120> in the middle chamber, i.e. it did not include the propeller stirrer ⁇ 121> shown in Figure 1 (and thus also not the motor ⁇ 122> and the translator ⁇ 124>).
- the connection between the middle and anode chamber was made by a hose that was attached to the bottom of the electrolytic cell.
- the anode compartment and middle compartment were separated by a 2.83 cm 2 anion exchange membrane (Tokuyama AMX, ammonium groups on polymer).
- the cathode and middle chamber were separated by a ceramic of the NaSICON type with an area of 2.83 cm 2 .
- the ceramic had a chemical composition of the formula Na34Zr20Si24P06O12.
- the anolyte was transferred to the anode compartment through the middle compartment.
- the flow rate of the anolyte was 1 l/h, that of the catholyte was 90 ml/h and a current of 0.14 A was applied.
- the temperature was 35°C.
- the electrolysis was carried out for 500 hours with the voltage remaining constant at 5V.
- Comparative example 1 was repeated with a two-chamber cell comprising only an anode and a cathode chamber, the anode chamber being separated from the cathode chamber by the ceramic of the NaSICON type.
- this electrolytic cell did not contain a center chamber. This is reflected in an even more rapid corrosion of the ceramic compared to comparative example 1, which leads to a rapid rise in the stress curve. With an initial value of the voltage of ⁇ 5 V, this increases to > 20 V within 100 hours.
- Comparative example 1 is repeated, with the central chamber comprising a propeller stirrer ⁇ 121>, which is aligned parallel to the NASICON solid electrolyte.
- the uniform flow of electrolyte through the center chamber is disrupted and turbulence occurs in the electrolyte. This makes it difficult for a pH gradient to build up during electrolysis.
- Inventive example 2
- Comparative example 1 is repeated with the center chamber K ⁇ 103> comprising a cross-shaped magnetic stir bar ⁇ 123-1> operated by a magnetic stirrer drive ⁇ 123-2>.
- This arrangement also disrupts the uniform flow of electrolyte through the center chamber and creates turbulence. This makes it difficult for a pH gradient to build up during electrolysis.
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Description
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CN202280046251.6A CN117597470A (zh) | 2021-06-29 | 2022-06-22 | 用于生产碱金属醇盐的三室电解池 |
KR1020237045182A KR20240023532A (ko) | 2021-06-29 | 2022-06-22 | 알칼리 금속 알콕사이드의 제조를 위한 3-챔버 전해 셀 |
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EP21182468.5A EP4112779B1 (de) | 2021-06-29 | 2021-06-29 | Dreikammerelektrolysezelle zur herstellung von alkalimetallalkoholaten |
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KR (1) | KR20240023532A (de) |
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-
2021
- 2021-06-29 DK DK21182468.5T patent/DK4112779T3/da active
- 2021-06-29 HU HUE21182468A patent/HUE064033T2/hu unknown
- 2021-06-29 EP EP21182468.5A patent/EP4112779B1/de active Active
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2022
- 2022-06-22 WO PCT/EP2022/066937 patent/WO2023274794A1/de active Application Filing
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KR20240023532A (ko) | 2024-02-22 |
CN117597470A (zh) | 2024-02-23 |
EP4112779A1 (de) | 2023-01-04 |
EP4112779B1 (de) | 2023-08-16 |
DK4112779T3 (da) | 2023-11-06 |
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