EP4134472A1 - Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse - Google Patents
Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse Download PDFInfo
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- EP4134472A1 EP4134472A1 EP21191300.9A EP21191300A EP4134472A1 EP 4134472 A1 EP4134472 A1 EP 4134472A1 EP 21191300 A EP21191300 A EP 21191300A EP 4134472 A1 EP4134472 A1 EP 4134472A1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims description 15
- 239000002184 metal Substances 0.000 title claims description 15
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 19
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 68
- 238000009792 diffusion process Methods 0.000 claims abstract description 50
- 239000013598 vector Substances 0.000 claims abstract description 49
- 230000005484 gravity Effects 0.000 claims abstract description 46
- 239000000919 ceramic Substances 0.000 claims abstract description 45
- 150000001768 cations Chemical class 0.000 claims abstract description 43
- 238000005192 partition Methods 0.000 claims abstract description 39
- 230000004888 barrier function Effects 0.000 claims abstract description 35
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 100
- 238000000034 method Methods 0.000 claims description 80
- -1 alkali metal alkoxide Chemical class 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 150000004820 halides Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 40
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 150000001450 anions Chemical class 0.000 abstract description 10
- 241000047703 Nonion Species 0.000 abstract description 6
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 43
- 210000004379 membrane Anatomy 0.000 description 39
- 239000007789 gas Substances 0.000 description 38
- 230000008569 process Effects 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 22
- 235000002639 sodium chloride Nutrition 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 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 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 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
- 239000002253 acid Substances 0.000 description 3
- 230000001174 ascending effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000003842 bromide salts Chemical class 0.000 description 3
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 230000000630 rising effect Effects 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene 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
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 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
- 229920001971 elastomer Polymers 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010327 methods by industry Methods 0.000 description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 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
- 229910052697 platinum 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
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000005060 rubber 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
- 241000894007 species Species 0.000 description 2
- 229920003934 Aciplex® Polymers 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
- 229920003935 Flemion® Polymers 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 244000089486 Phragmites australis subsp australis Species 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids 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
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 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
- 238000005553 drilling 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 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
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 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
- C25B9/01—Electrolytic cells characterised by shape or form
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- 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
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- 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
-
- 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 a method for producing an alkali metal alkoxide solution L 1 in an electrolytic cell E.
- the electrolytic cell E comprises at least one cathode chamber K K , at least one anode chamber K A and optionally a middle chamber K M located in between.
- the interior I KK of the cathode chamber K K is separated by a partition wall W comprising at least one cation-conducting solid electrolyte ceramic F A , for example NaSICON, from the interior I KA of the anode chamber K A or, in cases where the electrolytic cell E comprises a central chamber K M , from Interior I KM of the middle chamber K M separated.
- the electrolytic cell E comprises a central chamber K M
- the interior I KM of the central chamber K M is separated from the interior I KA of the anode chamber K A by a diffusion barrier D, for example a membrane selective for cations or anions or a non-ion-specific partition.
- the part O EA of the upper side O E delimiting the interior I KA of the anode chamber K A is essentially designed as a plane whose normal N OEA forms an angle 0° ⁇ EA ⁇ 45° to the gravitational vector V S .
- the sequence A KA is then arranged on the upper half of O EA .
- the part O EK of the upper side O E delimiting the interior I KK of the cathode chamber K K is essentially designed as a plane whose normal N OEK forms an angle 0° ⁇ EK ⁇ 45° to the gravity vector V S , and the sequence A KK is then arranged on the upper half of O EK .
- the electrochemical production of alkali metal alkoxide solutions is an important industrial process that is used, for example, in DE 103 60 758 A1 , the U.S. 2006/0226022 A1 and the WO 2005/059205 A1 is described.
- the principle of this process is reflected in an electrolytic cell in whose anode chamber there is a solution of an alkali salt, for example common salt or NaOH, and in whose cathode chamber there is the alcohol in question or a low-concentration alcoholic solution of the alkali metal alcoholate in question, for example sodium methoxide or sodium ethoxide.
- the cathode chamber and the anode chamber are separated by a ceramic that conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
- a current is applied, chlorine is formed at the anode - if a chloride salt of the alkali metal is used - and hydrogen and alcohol ions are formed at the cathode.
- 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 metal alcoholate in the cathode chamber and the concentration of the sodium ions in the anolyte decreases.
- 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 TiO 2 and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally converted electrolytically to form elemental 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 are converted into glycerol and the respective alkali metal hydroxide with electrolytically produced protons.
- the object of the present invention was therefore to provide a process for preparing an alkali metal alkoxide solution in an electrolytic cell which does not have this disadvantage.
- a further disadvantage of conventional electrolytic cells in this technical field results from the fact that the solid electrolyte is not stable over the long term with respect to aqueous acids. This is problematic insofar as the pH drops in the anode chamber during electrolysis as a result of oxidation processes (for example when halogens are produced by disproportionation or by oxygen formation). These acidic conditions attack the NaSICON solid electrolyte, so the process cannot be used on an industrial scale.
- Various approaches have been described in the prior art to address this problem.
- WO 2012/048032 A2 and US 2010/0044242 A1 describe, for example, electrochemical processes for the production of 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.
- the 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 to obtain sodium hypochlorite.
- the DE 42 33 191 A1 describes the electrolytic production of alcoholates from salts and alcoholates in multi-chamber cells and stacks of several cells.
- the 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 A similar arrangement is described in WO 2009/073062 A1 .
- this arrangement has the disadvantage that it is the alkali metal alkoxide solution, which is consumed as a buffer solution and is continuously contaminated is the desired product.
- 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.
- a further object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide. 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.
- the same electrolytic cell is shown in both figures from a different perspective 1 A shown perspective corresponds to the top view of the in Fig. 1B shown electrolytic cell E ⁇ 1> in the direction of arrow ⁇ 30>.
- the electrolytic cell E ⁇ 1> comprises a cathode chamber K K ⁇ 12> and an anode chamber K A ⁇ 11>.
- the anode chamber K A ⁇ 11> comprises an anodic electrode E A ⁇ 113> in the interior I KA ⁇ 112>, an inlet Z KK ⁇ 110> and an outlet A KA ⁇ 111>.
- the cathode chamber K K ⁇ 12> comprises a cathodic electrode E K ⁇ 123> in the interior I KK ⁇ 122>, an inlet Z KK ⁇ 120> and an outlet A KK ⁇ 121>.
- the electrolytic cell E ⁇ 1> forms a container B E ⁇ 800> on the side and on the bottom and a flat upper side O E ⁇ 801> on top.
- the interior I KA ⁇ 112> is delimited by a part O EA ⁇ 8011> of the upper side O E ⁇ 801> and a part B EA ⁇ 8001> of the container B E ⁇ 800>.
- the interior I KK ⁇ 122> is delimited by a part O EK ⁇ 8012> of the upper side O E ⁇ 801> and a part B EK ⁇ 8002> of the container B E ⁇ 800>.
- the interior I KK ⁇ 122> is also separated from the interior I KA ⁇ 112> by a partition wall W ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte FA ⁇ 18> that is selectively permeable for sodium ions.
- the NaSlCON solid electrolyte FA ⁇ 18> extends over the entire depth and height of the two-chamber cell E.
- the NaSlCON solid electrolyte FA ⁇ 18> contacts the two interior spaces I KK ⁇ 122> and I KA ⁇ 112> directly, so that sodium ions can be conducted from one interior to the other through the NaSICON solid electrolyte F A ⁇ 18>.
- the electrolytic cell E ⁇ 1> is inclined, which means that the flat upper side O E ⁇ 801> and thus also the two parts O EA ⁇ 8011> and O EK ⁇ 8012> are inclined.
- the angle ⁇ EA or ⁇ EK of the respective normal N OEA ⁇ 91> and N OEK ⁇ 92> of the plane O EA ⁇ 8011> and O EK ⁇ 8012> compared to the vector of gravity V s ⁇ 90> is ⁇ 25 °.
- the two drains A KA ⁇ 111> and A KK ⁇ 121> are located close to the highest edge of the electrolytic cell E ⁇ 1>.
- An aqueous solution of sodium chloride L 3 ⁇ 23> with pH 10.5 is added counter to gravity into the interior I KA ⁇ 112> via the inlet Z KA ⁇ 110>.
- a solution of sodium methoxide in methanol L 2 ⁇ 22> is fed into the interior space I KK ⁇ 122> via the inlet Z KK ⁇ 120>.
- a voltage is applied between the cathodic electrode E K ⁇ 123> and the anodic electrode E A ⁇ 113>.
- methanol is reduced to methoxide and H 2 in the electrolyte L 2 ⁇ 22> (CH 3 OH + e - ⁇ CH 3 O - + 1 ⁇ 2 H 2 ).
- Sodium ions diffuse from the interior I KA ⁇ 112> through the NaSICON solid electrolyte FA ⁇ 18> into the interior I KK ⁇ 122>.
- gases that form e.g. chlorine gas in the anode chamber K A ⁇ 11 > And hydrogen gas in the cathode chamber K K ⁇ 12>
- the rapid removal of the chlorine gas also reduces the acid-forming reaction Cl 2 + H 2 O ⁇ HOCl + HCl and thus the increase in acidity in the anode chamber K A ⁇ 11 >, which in turn extends the service life of the NaSICON solid electrolyte.
- the same electrolytic cell is shown in both figures from a different perspective Fig. 2A
- the perspective shown corresponds to the top view of the in Fig. 2B shown electrolytic cell E ⁇ 1> in the direction of arrow ⁇ 30>.
- the three-chamber electrolytic cell E comprises a cathode chamber K K ⁇ 12>, an anode chamber K A ⁇ 11> and a middle chamber K M ⁇ 13> located in between.
- the anode chamber K A ⁇ 11> comprises an anodic electrode E A ⁇ 113> in the interior I KA ⁇ 112>, an inlet Z KK ⁇ 110> and an outlet A KA ⁇ 111>.
- the cathode chamber K K ⁇ 12> comprises a cathodic electrode E K ⁇ 123> in the interior I KK ⁇ 122>, an inlet Z KK ⁇ 120> and an outlet A KK ⁇ 121>.
- the central chamber K M ⁇ 13> comprises an interior space I KM ⁇ 132>, an inlet Z KM ⁇ 130> and an outlet A KM ⁇ 131>.
- the interior space I KA ⁇ 112> is connected to the interior space I KM ⁇ 132> via the connection V AM ⁇ 15>.
- the electrolytic cell E ⁇ 1> forms a container B E ⁇ 800> on the side and on the bottom and a flat upper side O E ⁇ 801> on top.
- the interior I KA ⁇ 112> is delimited by a part O EA ⁇ 8011> of the upper side O E ⁇ 801> and a part B EA ⁇ 8001> of the container B E ⁇ 800>.
- the interior I KK ⁇ 122> is defined by a part O EK ⁇ 8012> of the upper side O E ⁇ 801> and a part B EK ⁇ 8002> of container B E ⁇ 800> limited.
- the interior space I KM ⁇ 132> is delimited by a part O EM ⁇ 8013> of the upper side O E ⁇ 801> and a part B EM ⁇ 8003> of the container B E ⁇ 800>.
- the interior I KK ⁇ 122> is also separated from the interior I KM ⁇ 132> by a partition W ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte FA ⁇ 18> that is selectively permeable for sodium ions.
- the NaSlCON solid electrolyte FA ⁇ 18> extends over the entire depth and height of the three-chamber cell E.
- the NaSlCON solid electrolyte FA ⁇ 18> contacts the two inner spaces I KK ⁇ 122> and I KM ⁇ 132> directly, so that sodium ions can be conducted from one interior to the other through the NaSICON solid electrolyte F A ⁇ 18>.
- the interior I KM ⁇ 132> of the middle chamber K M ⁇ 13> is additionally separated from the interior I KA ⁇ 112> of the anode chamber KA ⁇ 11> by a diffusion barrier D ⁇ 14>.
- the NaSlCON solid electrolyte F A ⁇ 18> and the diffusion barrier D ⁇ 14> extend over the entire depth and height of the three-chamber cell E.
- the diffusion barrier D ⁇ 14> is a cation exchange membrane (sulfonated PTFE).
- connection V AM ⁇ 15> is formed outside the electrolytic cell E , in particular by a tube or hose, the material of which can be chosen from rubber, metal or plastic.
- liquid can be conducted from the interior I KM ⁇ 132> of the central chamber K M ⁇ 13> into the interior I KA ⁇ 112> of the anode chamber KA ⁇ 11> outside the three-chamber cell E ⁇ 1>.
- connection V AM ⁇ 15> connects an outlet A KM ⁇ 131>, which breaks through the container B E ⁇ 800> of the electrolytic cell E at the bottom of the central chamber K M ⁇ 13>, with an inlet Z KA ⁇ 110>, which is at the bottom of the anode chamber K A ⁇ 11> breaks through the container B E ⁇ 800> of the electrolytic cell E.
- the electrolytic cell E ⁇ 1> is inclined, which means that the flat upper side O E ⁇ 801> and thus also the two parts O EA ⁇ 8011> and O EK ⁇ 8012> are inclined.
- the two drains A KA ⁇ 111> and A KK ⁇ 121> are located close to the highest edge of the electrolytic cell E ⁇ 1>.
- the angle ⁇ EA or ⁇ EK of the respective normal N OEA ⁇ 91> and N OEK ⁇ 92> of the plane O EA ⁇ 8011> and O EK ⁇ 8012> compared to the vector of gravity V S ⁇ 90> is ⁇ 25 °.
- An aqueous solution of sodium chloride L 3 ⁇ 23> with pH 10.5 is added via the inlet Z KM ⁇ 130> in the same direction as gravity into the interior I KM ⁇ 132> of the central chamber K M ⁇ 13>.
- the interior space I KM ⁇ 132 is formed by the connection V AM ⁇ 15>, which is formed between the outlet A KM ⁇ 131> of the central chamber K M ⁇ 13> and an inlet Z KA ⁇ 110> of the anode chamber KA ⁇ 11>> of the middle chamber K M ⁇ 13> connected to the interior I KA ⁇ 112> of the anode chamber K A ⁇ 11>.
- Sodium chloride solution L 3 ⁇ 23> is conducted through this connection V AM ⁇ 15> from interior I KM ⁇ 132> to interior I KA ⁇ 112>.
- a solution of sodium methoxide in methanol L 2 ⁇ 22> is fed into the interior space I KK ⁇ 122> via the inlet Z KK ⁇ 120>.
- a voltage is applied between the cathodic electrode E K ⁇ 123> and the anodic electrode E A ⁇ 113>.
- methanol in the electrolyte L 2 ⁇ 22> is reduced to methoxide and H 2 (CH 3 OH + e - ⁇ CH 3 O - + 1 ⁇ 2 H 2 ).
- Sodium ions diffuse from the interior I KM ⁇ 132> of the middle chamber K M ⁇ 103> through the NaSICON solid electrolyte FA ⁇ 18> into the interior I KK ⁇ 122>.
- the acidity would damage the NaSICON solid electrolyte FA ⁇ 18>, but is limited to the anode chamber KA ⁇ 11> by the arrangement in the three-chamber cell and is thus kept away from the NaSICON solid electrolyte FA ⁇ 18> in the electrolytic cell E. This increases its lifespan considerably.
- gases that form e.g. chlorine gas in the anode chamber K A ⁇ 11 > And hydrogen gas in the cathode chamber K K ⁇ 12>
- the rapid removal of the chlorine gas also reduces the acid-forming reaction Cl 2 + H 2 O ⁇ HOCl + HCl and thus the increase in acidity in the anode chamber K A ⁇ 11 >, which in turn extends the service life of the NaSICON solid electrolyte.
- This is carried out in an electrolytic cell E ⁇ 1>, which corresponds to the electrolytic cell E ⁇ 1> shown in Figures 2 A and 2 B with the following difference:
- the connection V AM ⁇ 15> from the interior I KM ⁇ 132> of the middle chamber K M ⁇ 13> to the interior I KA ⁇ 112> of the anode chamber K A ⁇ 11> is not outside, but through a perforation in the diffusion barrier D ⁇ 14> formed within the electrolytic cell E ⁇ 1>.
- This perforation can be introduced into the diffusion barrier D ⁇ 14> subsequently (e.g. by punching, drilling) or are already present in the diffusion barrier D ⁇ 14> from the outset due to the production thereof (e.g. in the case of textile fabrics such as filter cloths or metal fabrics).
- Figure 4 shows a further embodiment of the method according to the invention. It shows the method according to the invention using an electrolytic cell E ⁇ 1>, which is a two-chamber cell.
- the top is O E ⁇ 801> in the electrolytic cell E ⁇ 1> in 4 not parallel to the ground, and the interiors I KK ⁇ 122> and I KA ⁇ 112> have a trapezoidal section.
- the angle ⁇ EA or ⁇ EK of the respective normal N OEA ⁇ 91> and N OEK ⁇ 92> of the plane O EA ⁇ 8011> and O EK ⁇ 8012> compared to the vector of gravity V s ⁇ 90> is ⁇ 11 °.
- Figure 5 shows a further embodiment of the method according to the invention. It shows the method according to the invention using an electrolytic cell E ⁇ 1>, which is a three-chamber cell.
- the top is O E ⁇ 801> in the electrolytic cell E ⁇ 1> in figure 5 not parallel to the ground, and the interiors I KK ⁇ 122>, I KA ⁇ 112> and I KM ⁇ 132> have a trapezoidal section.
- the angle ⁇ EA or ⁇ EK of the respective normals N OEA ⁇ 91> and N OEK ⁇ 92> the plane O EA ⁇ 8011> and O EK ⁇ 8012> compared to the vector of gravity V S ⁇ 90> is ⁇ 11°.
- Figure 6 shows an embodiment of the method not according to the invention.
- a two-chamber electrolytic cell E is used as described for Figures 1 A and 1 B, except that these are not inclined and the two processes A KA ⁇ 111 > and A KK ⁇ 121 > in is arranged in the middle of the respective plane O EA ⁇ 8011> and O EK ⁇ 8012>.
- Figure 7 shows an embodiment of the method not according to the invention.
- a three-chamber electrolytic cell E is used as described for Figures 2 A and 2 B, except that these are not inclined and the two processes A KA ⁇ 111 > and A KK ⁇ 121 > in is arranged in the middle of the respective plane O EA ⁇ 8011> and O EK ⁇ 8012>.
- the method according to the invention is carried out in an electrolytic cell E.
- the electrolytic cell E comprises at least one anode chamber K A and at least one cathode chamber K K and optionally at least one intermediate chamber K M .
- This also includes electrolytic cells E which have more than one anode chamber K A and/or more than one cathode chamber K K and/or more than one middle chamber K M .
- Such electrolytic cells, in which these chambers are joined together in a modular manner, are, for example, in DD 258 143 A3 and the U.S. 2006/0226022 A1 described.
- the electrolytic cell E comprises an anode chamber K A and a cathode chamber K K and optionally a middle chamber K M located in between.
- the electrolytic cell E forms a container B E and a top O E from.
- the container B E and the upper side O E each comprise, independently of one another, in particular a material which is selected from the group consisting of steel, preferably rubberized steel, plastic, which is in particular made from Telene® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C ( post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride).
- the container B E and the top O E preferably comprise the same material. Even more preferably, they are then at least partially in one piece, ie at least part of the container B E forms one piece with at least part of the upper side O E .
- the container B E and the top O E are perforated in particular for inlets and outlets.
- the container B E and the top O E form the outer wall W A of the electrolytic cell E.
- the at least one anode chamber K A Within BE and OE are the at least one anode chamber K A , the at least one cathode chamber K K and, in the embodiments in which the electrolytic cell E comprises such, the at least one intermediate intermediate chamber K M .
- the container B E forms the bottom and the side walls of the electrolytic cell E.
- the container B E thus also forms the bottom and the side walls of the at least one anode chamber K A that it encompasses, of the at least one cathode chamber K K that it encompasses and in the embodiments ,
- the electrolytic cell E includes such a cell, which includes at least one intermediate chamber K M .
- the base preferably essentially forms a plane, and each of the side walls in each case more preferably also essentially forms a plane.
- the upper side O E is in particular formed essentially as a plane. "Top" implies that the lowest point of the plane defined by the top O E is higher (i.e. further from the center of the earth) than the lowest point of the container B E .
- the container B E and the top O E essentially form a polyhedron, preferably a hexahedron, in which at least one pair, preferably at least two pairs of opposite sides are parallel to one another. Even more preferably, the container B E and the top O E essentially form a cuboid.
- the electrolytic cell E is then arranged so that there is a face of the polyhedron on which the highest point (ie furthest from the center of the earth) of the polyhedron lies and whose lowest point is higher than the lowest point of the remaining sides. In this embodiment, this surface is then the upper side O E of the electrolytic cell E, the remaining surfaces form the container B E .
- the cathode chamber K K has at least one inlet Z KK , at least one outlet A KK and an interior space I KK , which includes a cathodic electrode E K .
- the interior I KK is delimited by a part O EK of the upper side O E and a part B EK of the container B E . Accordingly, the part of the upper side O E that delimits I KK is referred to as O EK , and the part of the container B E that delimits I KK is referred to as B EK .
- the interior I KK of the cathode chamber K K is separated by the partition W from the interior I KA of the anode chamber K A if the electrolytic cell E does not include a central chamber K M .
- the partition W comprises at least one solid electrolyte ceramic F A which conducts alkali cations, and the solid electrolyte ceramics which conduct alkali cations comprised by the partition W then contact the interior space I KK and the interior space I KA directly.
- the interior I KK of the cathode chamber K K is separated by the partition W from the interior I KM of the middle chamber K M if the electrolytic cell E comprises at least one middle chamber K M .
- the solid electrolyte ceramics which conduct alkali cations and are enclosed by the partition W then make direct contact with the interior space I KK and the interior space I KM .
- the partition wall W comprises at least one solid electrolyte ceramic F A which conducts alkali cations.
- the feature "partition wall” means that the partition wall W is liquid-tight.
- the dividing wall comprises either an alkali cation-conducting solid electrolyte ceramic that completely separates the interior space I KK and the interior space I KM or the interior space I KK and the interior space I KA from one another, or comprises several alkali cation-conducting solid electrolyte ceramics which, for example, adjoin one another without gaps.
- Contact directly means for the arrangement of the alkali cation-conducting solid electrolyte ceramics in the partition W and in the electrolytic cell E that there is an imaginary path from I KK to I AK or from I KK to I MK for each alkali cation-conducting solid electrolyte ceramic contained in the partition W There, which leads completely through the respective alkali cation-conducting solid electrolyte ceramic.
- any solid electrolyte through which cations, in particular alkali cations, more preferably sodium cations, can be transported from I AK to I KK or from I MK to I KK can be considered as the at least one solid electrolyte ceramic FA that conducts alkali cations.
- Such solid electrolytes are known to those skilled in the art and, for example, in DE 10 2015 013 155 A1 , in the WO 2012/048032 A2 , paragraphs [0035], [0039], [0040], in the US 2010/0044242 A1 , paragraphs [0040], [0041], in which DE 10360758 A1 , paragraphs [014] to [025].
- NaSICON LiSICON
- KSICON KSICON
- a sodium ion conductive solid electrolyte is preferred, more preferably having a NaSICON structure.
- NaSICON structures that can be used according to the invention are also described, for example, by Anantharamulu N, Koteswara Rao K, Rambabu G, Vijaya Kumar B, Velchuri Radha, Vithal M, J Mater Sci 2011, 46, 2821-2837 .
- the alkali cation-conducting solid electrolyte ceramics comprised by the dividing wall W independently of one another have a NaSICON structure of the formula M I 1+2w+x-y+z M II w MI II x Zr IV 2-wxy M V y (SiO 4 ) z (PO 4 ) 3-z on.
- M I is selected from Na + , Li + , preferably Na + .
- M II 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 III 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 alkali cation-conducting solid electrolyte ceramics comprised by the partition W have the same structure.
- the cathode chamber K K includes an interior space I KK , which in turn includes a cathodic electrode E K .
- a cathodic electrode E K Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the invention can be used as such a cathodic electrode E K .
- This electrode E K can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "balls”.
- the cathodic electrode E K comprises in particular a material which is selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium. E K preferably comprises nickel.
- the cathode chamber K K also includes an inlet Z KK and an outlet A KK .
- the inlet Z KK and the outlet A KK are attached to the cathode chamber K K in such a way that the liquid makes contact with the cathodic electrode E K as it flows through the interior I KK of the cathode chamber K K .
- the inlet Z KK and the outlet A KK can be attached to the electrolytic cell E by methods known to those skilled in the art, for example through holes in the container part B EK or the top part O EK and corresponding connections (valves) that allow the introduction or discharge of simplify fluid.
- the sequence A KK is arranged at O EK .
- the anode chamber K A has at least one inlet Z KA , at least one outlet A KA and an interior space I KA , which includes an anodic electrode E A .
- the interior I KA is delimited by a part O EA of the upper side O E and a part B EA of the container B E . Accordingly, the part of the top O E that delimits I KA is referred to as O EA and the part of the container B E that delimits I KA is referred to as B EA .
- the interior space I KA of the anode chamber K A is separated from the interior space I KM of the center chamber K M by a diffusion barrier D if the electrolytic cell E includes a central chamber K M . If the electrolytic cell E does not include a middle chamber K M , the interior space I KA of the anode chamber K is separated by the partition wall W from the interior space I KK of the cathode chamber K K .
- the anode chamber K A includes an interior space I KA , which in turn includes an anodic electrode E A .
- Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the third aspect of the invention can be used as such an anodic electrode E A .
- Such are in particular in WO 2014/008410 A1 , paragraph [024] or DE 10360758 A1 , paragraph [031].
- This electrode E A can consist of one layer or of several planar, mutually parallel layers, each of which can be perforated or expanded.
- the anodic electrode E A comprises in particular a material which is selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, noble metals such as platinum in particular, which is deposited on 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 preferably comprises a titanium anode (RuO 2 + IrO 2 /Ti) coated with ruthenium oxide/iridium oxide.
- the anode chamber K A also includes an inlet Z KA and an outlet A KA .
- the inlet Z KA and the outlet A KA are attached to the anode chamber K A in such a way that the liquid makes contact with the anodic electrode E A as it flows through the interior space I KA of the anode chamber K A .
- This is the prerequisite for the solution L 4 being obtained at the outlet A KA when the method according to the invention is carried out if the solution L 3 of a salt S is passed through the interior space I KA of the anode chamber KA .
- the inlet Z KA and the outlet A KA can be attached to the electrolytic cell E by methods known to those skilled in the art, e simplify fluid.
- the inlet Z KA can also lie within the electrolytic cell, for example as a perforation in the diffusion barrier D.
- the sequence A KA is arranged at O EA .
- the electrolytic cell E preferably has a central chamber K M .
- the optional middle chamber K M is located between the cathode chamber K K and the anode chamber K A . It comprises at least one inlet Z KM , at least one outlet A KM and an interior I KM .
- the interior I KM is delimited by a part O EM of the upper side O E and a part B EM of the container B E . Accordingly, the part of the top O E that delimits I KM is referred to as O EM and the part of the container B E that delimits I KM is referred to as B EM .
- the interior space I KA of the anode chamber K A is separated from the interior space I KM of the center chamber K M by a diffusion barrier D if the electrolytic cell E includes a central chamber K M .
- a KM is then also connected to the inlet Z KA by a connection V AM , so that liquid can be conducted from I KM into I KA through the connection V AM .
- the interior I KM of the optional central chamber K M is separated from the interior I KA of the anode chamber K A by a diffusion barrier D and from the interior I KK of the cathode chamber K K by the partition wall W.
- any material which is stable under the conditions of the method according to the invention and which prevents or slows down the transfer of protons from the liquid in the interior I KA of the anode chamber K A to the interior I KM of the optional middle chamber K M can be used for the diffusion barrier D.
- a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D.
- the diffusion barrier D 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 a textile fabric or metal fabric, particularly preferably a textile fabric.
- the textile fabric preferably comprises plastic, more preferably a plastic selected from PVC, PVC-C, polyvinyl ether (“PVE”), polytetrafluoroethylene (“PTFE”).
- the diffusion barrier D is a “membrane that is permeable to specific ions”, this means according to the invention that the respective membrane favors the diffusion of certain ions through it compared to other ions.
- membranes are meant that oppose the diffusion through them of ions of a certain type of charge favor 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 is a “membrane permeable to specific ions”, the diffusion barrier D 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 over 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 species 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 is a “membrane that is permeable to specific ions”, it is preferably an anion-conducting membrane because this prevents the diffusion of protons from the anode chamber K A into the middle chamber K M particularly well.
- 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 preferably chloride, is preferably used as the anion-conducting membrane.
- Anion-conducting membranes are, for example, from MA Hickner, AM Herring, EB Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51, 1727-1735 , by CG Arges, V Ramani, PN Pintauro, Electrochemical Society Interface 2010, 19, 31-35 , in WO 2007/048712 A2 as well as on Page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003 ) described.
- they have covalently bonded functional groups selected from -NH 3 + , -NRH 2 + , -NR 3 + , more preferably selected from -NH 3 + , -NR 3 + , even more preferably -NR 3 + .
- the diffusion barrier D is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S.
- the diffusion barrier D is even more preferably 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 even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -SO 3 - , -COO - , -PO 3 2- , -PO 2 H - , preferably -SO 3 - , (described in DE 10 2010 062 804 A1 , U.S. 4,831,146 ) carry.
- Neosepta ® membranes are described, for example, by SA Mareev, D.Yu. Butylskii, ND Pismenskaya, C Larchet, L Dammak, VV Nikonenko, Journal of Membrane Science 2018, 563, 768-776 .
- a cation-conducting membrane is used as the diffusion barrier D , this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula P NAFION , where n and m independently of one another are an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , more preferably is an integer from 10 2 to 10 4 .
- the optional middle chamber K M also includes an inlet Z KM and an outlet A KM . This makes it possible to add liquid, such as solution L 3 , to the interior space I KM of the middle chamber K M , and to transfer liquid therein, such as solution L 3 , to the anode chamber K A .
- the inlet Z KM and the outlet A KM can be attached to the electrolytic cell E by methods known to those skilled in the art, for example through holes in the container part B EM or the top part O EM and corresponding connections (valves) that allow the introduction or discharge of simplify fluid.
- the drain A KM can also be within the electrolytic cell, for example as a perforation in the diffusion barrier D.
- Bottom of the electrolytic cell E is, according to the invention , the side of the electrolytic cell E through which a solution (e.g. L 3 at A KM in Figure 2A) in the same direction as gravity exits the electrolytic cell E or the side of the electrolytic cell E through which a solution (e.g. L 2 at Z KK in Figures 1 A, 2 A and 3 A and L 3 at A KA in Figures 1 A and 2 A) is fed to the electrolytic cell E against the force of gravity.
- a solution e.g. L 3 at A KM in Figure 2A
- a solution e.g. L 2 at Z KK in Figures 1 A, 2 A and 3 A and L 3 at A KA in Figures 1 A and 2 A
- top O E of the electrolytic cell E is the side of the electrolytic cell E through which a solution (e.g. L 4 at A KA and L 1 at A KK in all figures) escapes from the electrolytic cell E against the force of gravity or the side of the Electrolytic cell E, through which a solution (eg L 3 at Z KM in Figures 2 A, 2 B, 3 A, 3 B and 4) is fed to the electrolytic cell E in the same direction as gravity.
- a solution e.g. L 4 at A KA and L 1 at A KK in all figures
- the dividing wall W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramics, which conduct alkali cations and are enclosed by the dividing wall W , make direct contact with the interior space I KK on the side S KK .
- the partition W is arranged in the electrolytic cell E in such a way that when the interior space I KK is completely filled with solution L 4 on the side S KK , the solution L 4 contacts all of the solid electrolyte ceramics contained in the partition W that conduct alkali cations , so that ions (eg alkali metal ions such as sodium, lithium) from all solid electrolyte ceramics which conduct alkali cations and are encompassed by the partition W can enter the solution L 4 .
- ions eg alkali metal ions such as sodium, lithium
- the dividing wall W is arranged in the embodiments in which the electrolytic cell E does not include a middle chamber K M in the electrolytic cell E such that the solid electrolyte ceramics enclosing the dividing wall W make direct contact with the interior space I KA .
- the partition wall W borders on the interior space I KA of the anode chamber K A .
- the dividing wall W is arranged in the electrolytic cell E in such a way that when the interior space I KA is completely filled with solution L 3 , the solution L 3 then contacts all of the solid electrolyte ceramics that conduct alkali cations that are contained in the dividing wall W , so that ions (for example, alkali metal ions such as sodium, lithium) from the solution L 3 in any alkali cation-conducting solid electrolyte ceramic, which is comprised of the partition W , can occur.
- ions For example, alkali metal ions such as sodium, lithium
- the dividing wall W is arranged in the electrolytic cell E in cases in which the electrolytic cell E comprises at least one central chamber K M such that the solid electrolyte ceramics which are comprised of the dividing wall W and which conduct alkali cations make direct contact with the interior space I KM .
- the partition wall W borders on the interior space I KM of the central chamber K M .
- the dividing wall W is arranged in the electrolytic cell E in such a way that when the interior space I KM is completely filled with solution L 3 , the solution L 3 then contacts all of the solid electrolyte ceramics that conduct alkali cations that are contained in the dividing wall W , so that ions (eg alkali metal ions such as sodium, lithium) from the solution L 3 can enter any alkali cation-conducting solid electrolyte ceramic, which is comprised of the partition W.
- ions eg alkali metal ions such as sodium, lithium
- the present invention relates to a process for preparing a solution L 1 of an alkali metal alkoxide XOR in the alcohol ROH, where X is an alkali metal cation and R is an alkyl radical having 1 to 4 carbon atoms.
- the process is carried out in an electrolytic cell E.
- R is preferably selected from the group consisting of n -propyl, iso -propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.
- the steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) running simultaneously are carried out.
- step (a1) a solution L 2 comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through I KK .
- the solution L 2 is preferably free of water.
- “free of water” means that the weight of the water in the solution L 2 based on the weight of the alcohol ROH in the solution L 2 (mass ratio) is ⁇ 1:10, more preferably ⁇ 1:20, even more preferably ⁇ 1:100 , more preferably ⁇ 0.5:100.
- the mass fraction of XOR in the solution L 2 is in particular >0 to 30% by weight, preferably 5 to 20% by weight, even more preferably at 10 to 20% by weight, more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
- the mass ratio of XOR to alcohol ROH in the solution L 2 is in particular in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20, even more preferably in the range 1:12 to 1:8, more preferably at 1:10.
- step (a2) a neutral or alkaline, aqueous solution L 3 of a salt S comprising X as a cation is passed through I KA .
- 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 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 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 .
- step (a3) a voltage is then applied between E A and E K .
- 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 specific voltages via voltage converters.
- the area of the solid electrolyte that contacts the anolyte in the interior I KA 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 (a3) of the method is carried out when the interior space I KA is at least partially loaded with L 3 and the interior space I KK is at least partially loaded with L 2 , so that both L 3 and L 2 contact the solid electrolyte ceramics, which are conductive to alkali cations and are enclosed by the partition W.
- step (a3) The fact that charge transport takes place between E A and E K in step (a3) implies that I KK and I KA are simultaneously charged with L 2 and L 3 , respectively, in such a way that they cover the electrodes E A and E K to such an extent that the circuit is closed.
- step (a1) and step (a2) are carried out continuously and voltage is applied in accordance with step (a3).
- the solution L 1 is obtained at the outlet A KK , the concentration of XOR in L 1 being higher than in L 2 .
- the concentration of XOR in L 1 is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, even more preferably 1077 to 1.4 fold, even more preferably 1077 to 1077 fold 1.08-fold higher than in L 2 , most preferably 1,077-fold higher than in L 2 , more preferably with the mass fraction of XOR in L 1 and in L 2 being in the range 10 to 20% by weight, even more preferably 13 to 14% by weight.
- the concentration of the cation X in the aqueous solution L 3 is preferably in the range from 3.5 to 5 mol/l, more preferably 4 mol/l.
- the concentration of the cation X in the aqueous solution L 4 is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 used in each case.
- steps (a1) to (a3) of the process are 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 formed in the interior I KK of the cathode chamber K K and is discharged from the cell via the outlet A KK can be discharged together with the solution L 1 .
- the mixture of hydrogen and solution L 1 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 together with the solution L 4 .
- oxygen and/or carbon dioxide can also be formed, which can also be removed.
- the mixture of chlorine, oxygen and/or CO 2 and solution L 4 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 , these can be separated from one another by methods known to those skilled in the art.
- steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) are carried out simultaneously.
- the electrolytic cell E comprises at least one middle chamber K M , and then the steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) running simultaneously are carried out.
- step ( ⁇ 1) a solution L 2 comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through I KK .
- the solution L 2 is preferably free of water.
- “free of water” means that the weight of the water in the solution L 2 based on the weight of the alcohol ROH in the solution L 2 (mass ratio) is ⁇ 1:10, more preferably ⁇ 1:20, even more preferably ⁇ 1:100 , more preferably ⁇ 0.5:100.
- the mass fraction of XOR in the solution L 2 is in particular >0 to 30% by weight, preferably 5 to 20% by weight, even more preferably at 10 to 20% by weight, more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
- the mass ratio of XOR to alcohol ROH in the solution L 2 is in particular in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20, even more preferably in the range 1:12 to 1:8, more preferably at 1:10.
- step ( ⁇ 2) a neutral or alkaline aqueous solution L 3 of a salt S comprising X as a cation is passed through I KM , then over V AM , then through I KA .
- 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 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 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 .
- step ( ⁇ 3) a voltage is then applied between E A and E K .
- 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 interior I KM of the middle chamber K M 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 , still more preferably 2.83 cm 2 .
- step ( ⁇ 3) of the method is carried out when both interior spaces I KM and I KA are at least partially loaded with L 3 and I KK is at least partially loaded with L 2 , so that both L 3 and L 2 also contact the solid electrolytes enclosed by the partition W.
- step ( ⁇ 3) The fact that charge transport takes place between E A and E K in step ( ⁇ 3) implies that I KK , I KM and I KA are simultaneously charged with L 2 and L 3 , respectively, in such a way that they connect the electrodes E A and E K so far that the circuit is closed.
- step ( ⁇ 1) and step ( ⁇ 2) are carried out continuously and voltage is applied in accordance with step ( ⁇ 3).
- the solution L 1 is obtained at the outlet A KK , the concentration of XOR in L 1 being higher than in L 2 .
- the concentration of XOR in L 1 is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, even more preferably 1077 to 1.4 fold, even more preferably 1077 to 1077 fold 1.08-fold higher than in L 2 , most preferably 1,077-fold higher than in L 2 , more preferably with the mass fraction of XOR in L 1 and in L 2 being in the range 10 to 20% by weight, even more preferably 13 to 14% by weight.
- the concentration of the cation X in the aqueous solution L 3 is preferably in the range from 3.5 to 5 mol/l, more preferably 4 mol/l.
- the concentration of the cation X in the aqueous solution L 4 is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 used in each case.
- steps ( ⁇ 1) to ( ⁇ 3) of the process are 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 interior I KK of the cathode chamber K K , which hydrogen can be discharged from the cell together with the solution L 1 via the outlet A KK .
- the mixture of hydrogen and solution L 1 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 together with the solution L 4 .
- oxygen and/or carbon dioxide can also be formed, which can also be removed.
- the mixture of chlorine, oxygen and/or CO 2 and solution L 4 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 , these can be separated from one another by methods known to those skilled in the art.
- Steps ( ⁇ 1) to ( ⁇ 3) of the method according to the invention protect the acid-labile solid electrolyte from corrosion without having to sacrifice alcoholate solution from the cathode space as a buffer solution, as in the prior art. These process steps are therefore more efficient than those in WO 2008/076327 A1 described procedure in which the product solution is used for the middle chamber, which reduces the overall turnover.
- condition (i), (ii) is/are fulfilled.
- condition (iii) described below is also met in cases in which the electrolytic cell E comprises at least one central chamber K M and the connection V AM is formed outside the electrolytic cell E.
- Normal N OEA in the sense of the invention refers to the normal line (ie orthogonal straight line) or else the normal vector (ie orthogonal vector) to the upper side O EA , which is essentially designed as a plane.
- the normal N OEA is therefore the vector or straight line which is perpendicular to the plane formed by the upper side O EA . This vector intersects the vector of gravity at the angle ⁇ EA .
- the angle ⁇ EA can be determined by intersecting the straight line that is perpendicular to the plane formed by the upper side O EA with a straight line that is parallel to the direction of gravity.
- the flow A KA is located on the upper half of O EA .
- a KA is attached to this upper half.
- the upper side O EA is inclined in relation to this, which means that the gases produced in the interior I KA are at the highest point of the interior due to the difference in density from the electrolyte I KA rise. This rising of the gases is facilitated by the fact that the upper side O EA is designed as a plane, in particular it does not have any steps or spikes in which gas bubbles could get caught.
- O EA is formed as a plane whose normal N OEA forms an angle ⁇ EA , where 0° ⁇ ⁇ EA ⁇ 45°, to the gravity vector V s , and the sequence A KA is on the upper half of O EA arranged.
- O EK is essentially a plane whose normal N OEK forms an angle ⁇ EK , where 0° ⁇ ⁇ EK ⁇ 45°, to the gravity vector V s , and the drain A KK is on the top half of O EK arranged.
- Normal N OEK in the sense of the invention refers to the normal straight line (ie orthogonal straight line) or also the normal vector (ie orthogonal vector) to the upper side O EK , which is essentially designed as a plane.
- the normal N OEK is accordingly the vector or the straight line which is perpendicular to the plane which is formed by the upper side O EK . This vector intersects the vector of gravity at the angle ⁇ EK .
- the angle ⁇ EK can be determined by intersecting the straight line that is perpendicular to the plane formed by the upper side O EK with a straight line that is parallel to the direction of gravity.
- the upper side O EK is because its normal N OEK forms an angle 0° ⁇ EK ⁇ 45° to the gravitational vector V s , inclined in relation to this, whereby gases arising in the interior I KK due to the density difference to the electrolyte reach the highest point of the interior I KK rise. This rising of the gases is facilitated by the fact that the upper side O EK is in the form of a plane, in particular it does not have any steps or spikes in which gas bubbles could get caught.
- O EK is formed as a plane whose normal N OEK forms an angle ⁇ EK , where 0° ⁇ ⁇ EK ⁇ 45°, to the gravity vector V s , and the sequence A KK is on the upper half of O EK arranged.
- drain A KA is located on the top half of O EA and drain A KK is located on the top half of O EK , more preferably then drain A KA is located on the top third of O EA and drain A KK on the top third of O EK , more preferably then drain A KA is located on the top quarter of O EA and drain A KK is located on the top quarter of O EK , more preferably then drain A KA is located on the top fifth of O EA and Flow A KK is located on the top fifth of O EK , more preferably then flow A KA is located on the top tenth of O EA and flow A KK is located on the top tenth of O EK .
- the combination of the two conditions (i) and (ii) prevents the formation of a gas cushion in the respective interior space I KK and I KA of the cathode chamber K K and anode chamber K A in a particularly efficient manner.
- O EM is essentially a plane whose normal N OEM forms an angle ⁇ EM , where 0° ⁇ ⁇ EM ⁇ 45°, to the gravity vector V s , and the gradient A KM is on the top half of O EM arranged.
- Normal N OEM in the sense of the invention refers to the normal line (ie orthogonal straight line) or also the normal vector (ie orthogonal vector) to the upper side O EM , which is essentially designed as a plane.
- the normal N OEM is the vector or line perpendicular to the plane formed by the top O EM . This vector intersects the vector of gravity at the angle ⁇ EM .
- the angle ⁇ EM can be determined by intersecting the straight line that is perpendicular to the plane formed by the upper side O EM with a straight line that is parallel to the direction of gravity.
- the upper side O EM is inclined in that its normal N OEM forms an angle 0° ⁇ EK ⁇ 45° to the gravity vector V s , which means that the gases produced in the interior I KM are at the highest due to the density difference Place of interior I KM rise. This rising of the gases is facilitated by the fact that the upper side O EM is in the form of a plane, in particular it does not have any steps or spikes in which gas bubbles could get caught.
- O EM is formed as a plane whose normal N OEM forms an angle ⁇ EM , where 0° ⁇ ⁇ EM ⁇ 45°, to the gravity vector V s , and the sequence A KM is on the upper half Arranged by O EM .
- NM Sodium methylate
- the electrolytic cell consisted of three chambers, as in Figure 7 shown. The electrolytic cell was not tilted so that the normal to the top of the electrolytic chamber was parallel to the gravity vector. The drains of the anode chamber and the cathode chamber were also found in the center of the top.
- 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 Na 3.4 Zr 2.0 Si 2.4 P 0.6 O 12 .
- 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.
- gas cushions form in the interior spaces of the cathode and anode chambers, in particular due to the formation of chlorine gas and hydrogen at the anode or cathode.
- 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.
- the arrangement corresponded to that in Figure 6 shown.
- this electrolytic cell did not contain a center chamber.
- the electrolytic cell was not tilted so that the normal to the top of the electrolytic chamber was parallel to the gravity vector.
- the drains of the anode chamber and the cathode chamber were also found in the center of the top.
- Comparative example 1 is repeated using an electrolytic cell according to Figures 2A and 2B which is tilted. The drains of the anode chamber and the cathode chamber were also found on the top near the highest edge.
- the gases produced in the anode and cathode chambers are quickly discharged from the electrolysis chamber at the outlet. This ensures that the interior volumes are not blocked by gas bubbles.
- the acidification process of the electrolytes, especially the anolyte is curbed.
- Comparative example 2 is repeated using an electrolytic cell according to Figures 1A and 1B which is tilted. The drains of the anode chamber and the cathode chamber were also found on the top near the highest edge.
- the gases produced in the anode and cathode chambers are quickly discharged from the electrolysis chamber at the outlet. This ensures that the interior volumes are not blocked by gas bubbles.
- the acidification process of the electrolytes, especially the anolyte is curbed.
- the inventive inclination of the upper side of the electrolytic cell in the area of the anode and cathode chambers and the inventive arrangement of the drains prevent the formation of a gas cushion in the respective interior space.
- the volumes of the interior spaces are completely available for the electrolytes and thus for the electrolysis, and there are no undesired increases in voltage.
- Gases (such as chlorine) produced at the respective electrode are quickly discharged, which prevents the electrolyte from acidifying and thus also protects the NaSICON ceramic.
- the use of the three-chamber cell in the method of the invention also prevents corrosion of the solid electrolyte while at the same time not sacrificing an alkali metal alkoxide product for the center chamber and keeping the voltage constant.
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EP21191300.9A EP4134472A1 (fr) | 2021-08-13 | 2021-08-13 | Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse |
EP22760747.0A EP4384656A1 (fr) | 2021-08-13 | 2022-08-03 | Procédé de production d'alcoolates de métal alcalin dans une cellule d'électrolyse |
PCT/EP2022/071856 WO2023016897A1 (fr) | 2021-08-13 | 2022-08-03 | Procédé de production d'alcoolates de métal alcalin dans une cellule d'électrolyse |
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EP4384656A1 (fr) | 2024-06-19 |
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