EP3885470A1 - Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres - Google Patents
Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres Download PDFInfo
- Publication number
- EP3885470A1 EP3885470A1 EP20165238.5A EP20165238A EP3885470A1 EP 3885470 A1 EP3885470 A1 EP 3885470A1 EP 20165238 A EP20165238 A EP 20165238A EP 3885470 A1 EP3885470 A1 EP 3885470A1
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- European Patent Office
- Prior art keywords
- chamber
- solution
- cation
- xor
- anode chamber
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Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims description 12
- 239000002184 metal Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000009792 diffusion process Methods 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 38
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 34
- 150000001768 cations Chemical class 0.000 claims abstract description 31
- 230000004888 barrier function Effects 0.000 claims abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- -1 NaSICON Chemical class 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 71
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 5
- 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
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 21
- 235000002639 sodium chloride Nutrition 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 230000005484 gravity Effects 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 239000000463 material 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
- 239000002253 acid Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 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
- 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 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
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
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- 238000013508 migration Methods 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 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
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 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
- 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
- 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 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
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 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
- 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
- 150000003842 bromide salts Chemical class 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
- 229910002092 carbon dioxide Inorganic materials 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
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 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
- 238000000909 electrodialysis Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 150000004694 iodide salts Chemical class 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
- 238000005259 measurement Methods 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
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 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
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
-
- 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
- C25B3/13—Organo-metallic 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
- C25B3/01—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
- 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
- C25B9/17—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
Definitions
- the present invention relates to a method for the electrochemical production of an alkali metal alcoholate solution.
- the process is carried out in an electrolysis cell which has three chambers, the middle chamber being separated from the cathode chamber by a solid electrolyte permeable to cations, e.g. NaSICON, and from the anode chamber by a diffusion barrier, e.g. a membrane selective for cations or anions.
- a solid electrolyte permeable to cations e.g. NaSICON
- a diffusion barrier e.g. a membrane selective for cations or anions.
- the electrochemical production of alkali metal alcoholate solutions is an important industrial process, for example in the DE 103 60 758 A1 , the US 2006/0226022 A1 and the WO 2005/059205 A1 is described.
- the principle of this process is an electrolysis cell in whose anode chamber the solution of an alkali salt, for example common salt or NaOH, and in whose cathode chamber the alcohol in question or a low-concentration alcoholic solution of the alkali alcoholate in question, for example sodium methoxide or sodium ethoxide, are located.
- the cathode chamber and the anode chamber are separated by a ceramic that conducts the alkali metal ion used, for example NaSICON or its analogues for potassium or lithium.
- 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 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 converted in a second step with electrolytically generated protons to glycerine and the respective alkali metal hydroxide.
- the prior art therefore describes processes that are carried out in electrolysis cells with an ion-permeable layer, such as NaSiCON solid electrolytes.
- these solid electrolytes typically have the disadvantage that they are not long-term stable to aqueous acids. This is problematic insofar as the pH drops in the anode chamber during electrolysis due to oxidation processes (for example when halogens are produced by disproportionation or by the formation of oxygen). These acidic conditions attack the NaSICON solid electrolyte, so that the process cannot be used on an industrial scale.
- oxidation processes for example when halogens are produced by disproportionation or by the formation of oxygen.
- three-chamber cells have been proposed in the prior art. Such are known in the electrodialysis field, for example US 6,221,225 B1 .
- 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 solid electrolyte such as NaSICON that is permeable to cations.
- solution from the cathode chamber for example, is supplied to the central chamber.
- 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 WO 2008/076327 A1 describes a process for the preparation of alkali metal alcoholates.
- a three-chamber cell is used, the middle chamber of which is filled with alkali metal alcoholate (see, for example, paragraphs [0008] and [0067] of WO 2008/076327 A1 ).
- the solid electrolyte separating the central chamber and the cathode chamber is protected from the solution in the anode chamber, which becomes more acidic during the electrolysis.
- this arrangement has the disadvantage that the alkali metal alcoholate solution is the desired product, but this is consumed as a buffer solution and continuously contaminated.
- the object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alcoholate which ensures protection of the cation-conducting solid electrolyte from acid, but does not have the aforementioned disadvantages.
- the process should be distinguished by a more economical use of the starting materials compared to the prior art.
- illustration 1 shows the method according to the invention on the basis of a three-chamber cell E ⁇ 100> comprising a cathode chamber K K ⁇ 102>, an anode chamber K A ⁇ 101> and a central chamber K M ⁇ 103> lying in between.
- the three chambers are bounded by an outer wall ⁇ 117> of the three-chamber cell E ⁇ 100>.
- the cathode chamber K K ⁇ 102> is also separated from the central chamber K M ⁇ 103> by a NaSICON solid electrolyte F K ⁇ 111> which is selectively permeable to sodium ions.
- the central chamber K M ⁇ 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>.
- a solution of sodium methoxide in methanol L 2 ⁇ 113> is passed through the cathode chamber K K ⁇ 102>.
- An aqueous solution of sodium chloride L 3 ⁇ 114> with pH 10.5 is fed into the middle chamber K M ⁇ 103> via the inlet Z KM ⁇ 108> in the same direction as the force of gravity.
- Sodium chloride solution L 3 ⁇ 114> is passed through this connection V AM ⁇ 112> from the middle chamber K M ⁇ 103> into the anode chamber K A ⁇ 101>.
- methanol is reduced to methanolate and H 2 in the cathode chamber K K ⁇ 102>.
- Sodium ions diffuse from the middle chamber K M ⁇ 103> through the NaSICON solid electrolyte F K ⁇ 111> into the cathode chamber K K ⁇ 102>.
- Figure 2 shows an embodiment of the method according to the invention, which is similar to that in illustration 1 shown corresponds. The only difference here is that the connection V AM ⁇ 112> from the central chamber K M ⁇ 103> into the anode chamber K A ⁇ 101> is formed by a perforation in the diffusion barrier D ⁇ 110>.
- Figure 3 shows a diagram of the voltage curve of the electrolysis in a three-chamber cell according to the invention in comparison with a two-chamber cell.
- the measurement points of the comparative example are shown with triangles ( ⁇ ), those of the example according to the invention with points (•).
- the x-axis shows the time in hours, while the y-axis shows the measured voltage in volts.
- the comparison shows that a constant voltage curve is obtained with the cell according to the invention, while the voltage increases rapidly in the two-chamber cell due to the destruction of the solid electrolyte.
- the inventive process is in an electrolysis cell E, which comprises at least one anode chamber K A, at least one cathode chamber K K and at least one intermediate fluid chamber K M is performed.
- electrolysis cells in which these chambers are joined together in a modular manner, are for example in the DD 258 143 A3 , US 2006/0226022 A1 described.
- the anode chamber K A comprises an anodic electrode E A.
- Any electrode familiar to the person skilled in the art that is stable under the conditions of the method according to the invention can be used as such anodic electrode E A.
- Such are especially in WO 2014/008410 A1 , Paragraph [024] or DE 10360758 A1 , Paragraph [031].
- This electrode E A can consist of one layer or consist of several planar layers parallel to one another, 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 in particular platinum, which is supported 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.
- Further possible anode materials are in particular stainless steel, lead, graphite, Tungsten carbide, titanium diboride.
- E A preferably comprises a titanium anode coated with ruthenium oxide / iridium oxide (RuO 2 + IrO 2 / Ti).
- the cathode chamber K K comprises a cathodic electrode E K.
- Any electrode familiar to the person skilled in the art that is stable under the conditions can be considered as such cathodic electrode E K. Such are especially in WO 2014/008410 A1 , Paragraph [025] or DE 10360758 A1 , Paragraph [030].
- This electrode E K can be selected from the group consisting of mesh wool, three-dimensional matrix structure or as “spheres”.
- 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 at least one middle chamber K M is located between the anode chamber K A and the cathode chamber K K.
- the electrolytic cell E usually has an outer wall W A.
- the outer wall W A is in particular made of a material which is selected from the group consisting of steel, preferably rubberized steel, plastic, in particular Telene® (thermoset polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride ) is selected, is selected.
- W A can be broken through in particular for inlets and outlets. Within W A are then at least one anode chamber K A, the at least one cathode chamber K K and the at least one intermediate fluid chamber K M.
- K M is separated by a diffusion barrier of D K A and separated by a cation-conducting solid electrolyte alkali F K K K.
- any material which is stable under the conditions of the method according to the invention and which prevents or slows the transfer of protons from the liquid in the anode chamber K A into the central chamber K M can be used as the diffusion barrier D.
- the diffusion barrier D is preferably a membrane that is permeable to specific ions.
- the material for the nonionic partition is selected in particular from the group consisting of fabric, which is in particular textile fabric or metal fabric, glass, which is in particular sintered glass or glass frits, ceramics, in particular ceramic frits, membrane diaphragms.
- the diffusion barrier D is a “membrane permeable to specific ions”, this means according to the invention that the respective membrane favors the diffusion of certain ions through it over others.
- the diffusion barrier D is preferably an anion-conducting membrane or a cation-conducting membrane.
- anion-conducting membranes are those which selectively conduct anions, preferably selectively certain anions. In other words, they favor the diffusion of anions through them over that of cations, in particular over protons, and even more preferably they also 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 certain cations. In other words, they favor the diffusion of cations through them over that of anions, more preferably they favor the diffusion of certain cations through them over the diffusion of other cations through them, even more preferably cations that are is not protons, even more preferably sodium cations, compared to protons.
- “Favor the diffusion of certain ions X over 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 10, preferably 100, preferably 1000 times higher as the diffusion coefficient of ion type Y for the membrane in question.
- anion-conducting membrane one which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
- anion-conducting membrane Such membranes are known to the person skilled in the art and can be used by him.
- Salt S is preferably a halide, sulfate, sulfite, nitrate, hydrogen carbonate 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.
- They preferably 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 which is selective for the cations comprised by the salt S.
- the diffusion barrier D is even more preferably an alkali-ion-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, polyether ketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are used as the cation-conducting membrane, 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 ) wear.
- Neosepta® membranes are described by, for example 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, for example, be a polymer functionalized with sulfonic acid groups, in particular of the following formula P NAFION , where n and m are, independently of one another, 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 .
- any solid electrolyte which can transport cations, in particular alkali cations, more preferably sodium cations, from the central chamber K M into the cathode chamber K K can be used as the solid electrolyte F K which conducts alkali cations.
- Such solid electrolytes are known to the person skilled in the art and, for example, in the 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 the DE 10360758 A1 , Paragraphs [014] to [025].
- NaSICON LiSICON
- KSICON KSICON
- a solid electrolyte F K which conducts sodium ions is preferred, this even more preferably having 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, M. Vithal, J Mater Sci 2011, 46, 2821-2837 .
- NaSICON preferably has a structure of the formula M I 1 + 2w + x-y + z M II w M III x Zr IV 2-wxy M V y (SiO 4 ) z (PO 4 ) 3-z .
- 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 chosen in this way that 1 + 2w + x - y + z ⁇ 0 and 2 - w - x - y ⁇ 0.
- the cathode chamber K K also includes an inlet Z KK and an outlet A KK , which makes it possible to add liquid, such as solution L 2 , to the cathode chamber K K and to add liquid located therein, such as solution L 1 remove.
- the inlet Z KK and the outlet A KK are attached to the cathode chamber K K in such a way that the solution contacts the cathodic electrode E K when it flows through the cathode chamber K K. This is the prerequisite that when the method according to the invention is carried out at the outlet A KK, the solution L 1 is obtained when the solution L 2 of an alkali metal alcoholate XOR in the alcohol ROH is passed through K K.
- the anode chamber K A also includes an outlet A KA , which makes it possible to remove liquid located in the anode chamber K A , for example the aqueous solution L 4.
- the central chamber K M includes an inlet Z KM , while K A and K M are connected to one another by a connection V AM.
- a solution L 3 can be added to K M and this can then be passed through K M , and via V AM into the anode chamber K A , then passed through this K A.
- V AM and the drain A KA are attached to the anode chamber K A in such a way that the solution L 3 contacts the anodic electrode E A as it flows through the anode chamber K A. This is the prerequisite that when the method according to the invention is carried out at the outlet A KA, the aqueous solution L 4 is obtained when the solution L 3 is first passed through K M , then V AM , then K A.
- Inlets Z KK , Z KM , Z KA and outlets A KK , A KA , A KM can be attached to the electrolysis cell by methods known to those skilled in the art.
- connection V AM can be formed inside the electrolytic cell E and / or outside the electrolytic cell E.
- connection V AM is formed within the electrolytic cell E , it is preferably formed by at least one perforation in the diffusion barrier D.
- connection V AM is formed outside the electrolytic cell E , it is preferably formed by a connection of K M and K A extending outside the electrolytic cell E , in particular by the fact that in the central chamber K M an outlet A KM through the outer wall W A is preferred at the bottom of the middle chamber K M , with the inlet Z KM being more preferably at the top of the middle chamber K M , and in the anode chamber K A an inlet Z KA through the outer wall W A , preferably at the bottom of the anode chamber K A , is formed, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
- the drain A KA is then even more preferred at the top of the anode chamber K A.
- Drain A KM at the bottom of the central chamber K M means that the drain A KM is attached to the electrolytic cell E in such a way that the solution L 3 leaves the central chamber K M in the same direction as the force of gravity.
- Inlet Z KA at the bottom of the anode chamber K A means that the inlet Z KA is attached to the electrolytic cell E in such a way that the solution L 3 enters the anode chamber K A against gravity.
- Inlet Z KM at the top of the middle chamber K M means that the inlet Z KM is attached to the electrolytic cell E in such a way that the solution L 3 enters the middle chamber K M in the same direction as the force of gravity.
- Drain A KA at the top of the anode chamber K A means that the drain A KA is attached to the electrolytic cell E in such a way that the solution L 4 leaves the anode chamber K A against gravity.
- This embodiment is particularly advantageous and therefore preferred when the outlet A KM is formed by the outer wall W A at the bottom of the central chamber K M and the inlet Z KA is formed by the outer wall W A at the bottom of the anode chamber K A.
- the outlet A KM is formed by the outer wall W A at the bottom of the central chamber K M and the inlet Z KA is formed by the outer wall W A at the bottom of the anode chamber K A.
- the direction of flow from L 3 in K M is opposite or in the same direction, preferably opposite to the direction of flow from L 3 in K A , depending on how the connection V AM is attached to the electrolytic cell E.
- the direction of flow from L 3 in K M is preferably in the same direction as the force of gravity.
- connection V AM is arranged between central chamber K M and anode chamber K A in such a way that at least part of the aqueous
- Solution L 3 more preferably the entire aqueous solution L 3 , the central chamber K M and the anode chamber K A flows completely through.
- connection V AM ⁇ 112> is formed outside the electrolysis cell E ⁇ 100>, this can be ensured in particular by the fact that Z KM ⁇ 108> and A KM ⁇ 118> on opposite sides of the outer wall W A ⁇ 117> of the central chamber K. M ⁇ 103> are arranged (i.e.
- Z KA ⁇ 119> and Z KM ⁇ 108> can be formed on the same side of the electrolytic cell E ⁇ 100>, A KM ⁇ 118> and A KA ⁇ 106> then also being formed automatically on the same side of the electrolytic cell E ⁇ 100> are.
- Z KA ⁇ 119> and Z KM ⁇ 108> be formed on opposite sides of the electrolytic cell E ⁇ 100>, A KM ⁇ 118> and A KA ⁇ 106> then also being formed automatically on opposite sides of the electrolytic cell E ⁇ 100> are.
- connection V AM ⁇ 112> is formed within the electrolytic cell E ⁇ 100>, this can be ensured in particular by the fact 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 in Figure 2 is the upper side, the inlet Z KM ⁇ 108> and the outlet A KA ⁇ 106> comprises and the diffusion barrier D ⁇ 110>, starting from this side A, extends into the electrolysis cell ⁇ 100>, but not all the way to that of the Side A opposite side ("side B") of the electrolytic cell E ⁇ 100>, which is then the bottom or the top of the electrolytic cell E ⁇ 100>, extends and thereby 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>, even more preferably 80% to 90%
- the “bottom of the electrolysis cell E” is the side of the electrolysis cell E through which a solution (eg L 3 ⁇ 114> at A KM ⁇ 118> in illustration 1 ) exits the electrolysis cell E in the same direction as gravity or the side of the electrolysis cell E through which a solution (e.g. L 2 ⁇ 113> at Z KK ⁇ 107> in Figures 1 and 2 and L 3 ⁇ 114> at A KA ⁇ 119> in illustration 1 ) is fed to the electrolytic cell E against gravity.
- a solution e.g. L 3 ⁇ 114> at A KM ⁇ 118> in illustration 1
- top of the electrolytic cell E is the side of the electrolytic cell E through which a solution (eg L 4 ⁇ 116> for A KA ⁇ 106> and L 1 ⁇ 115> for A KK ⁇ 109> in Figures 1 and 2) is opposite gravity exits the electrolysis cell E or the side of the electrolysis cell E through which a solution (e.g. L 3 ⁇ 114> at Z KM ⁇ 108> in Figures 1 and 2) is fed to the electrolysis cell E in the same direction as the force of gravity.
- a solution e.g. L 4 ⁇ 116> for A KA ⁇ 106> and L 1 ⁇ 115> for A KK ⁇ 109> in Figures 1 and 2
- the method according to the invention comprises the following steps (a), (b) and (c), which are carried out simultaneously.
- step (a) a solution L 2 comprising the alcohol ROH, preferably comprising an alkali metal alcoholate XOR in the alcohol ROH, is passed through K K.
- X is an alkali metal cation and R is an alkyl radical with 1 to 4 carbon atoms.
- 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 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) 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 solution L 2 is in particular in the range 1: 100 to 1: 5, more preferably in the range 1:25 to 3:20, even more preferably in the range 1:12 up to 1: 8, more preferably 1:10.
- step (b) a neutral or alkaline aqueous solution L 3 of a salt S comprising X as a cation is passed through K M , then through V AM , then through K A.
- the salt S is described above.
- the pH of the aqueous solution L 3 is 7.0, preferably in the range 7 to 12, more preferably in the range 8 to 11, even more preferably 10 to 11, most preferably 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 (c) a voltage is then applied between E A and E K.
- the charge source is known to the person skilled in the art and is typically a rectifier which converts alternating current into direct current and can generate certain voltages via voltage converters.
- This can be determined as standard by a person skilled in the art.
- the area of the solid electrolyte that contacts the anolyte located in the central 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 , even more preferably 2.83 cm 2 .
- step (c) is carried out in the process according to the invention when both chambers K M and K A are at least partially loaded with L 3 and K K is at least partially loaded with L 2.
- step (c) The fact that a charge transport takes place between E A and E K in step (c) implies that K K , K M and K A are simultaneously charged with L 2 and L 3 in such a way that they the electrodes E A and E Cover K to the extent that the electrical circuit is closed.
- step (a) and step (b) are carried out continuously and voltage is applied in accordance with step (c).
- 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 from 1.01 to 2.2 times, more preferably from 1.04 to 1.8 times, even more preferably from 1.077 to 1.4 times, even more preferably from 1.077 to 1.08 times higher than in L 2 , most preferably 1.077 times higher than in L 2 , the mass fraction of XOR in L 1 and in L 2 in the range from 10 to 20% by weight, even more preferred 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.
- the process according to 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 up 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 , which 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 in a particular embodiment of the present invention are 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 arise, which can be discharged from the cell together with the solution L 4 via the outlet A KK.
- oxygen and / or carbon dioxide can also arise, 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 the person skilled in the art.
- these can then be separated from one another by methods known to those skilled in the art.
- the method according to the invention protects 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.
- the method according to the invention is thus more efficient than that in WO 2008/076327 A1 described procedure, in which the product solution is used for the middle chamber, which reduces the total turnover.
- illustration 1 shows a preferred embodiment of the invention in a three-chamber cell E ⁇ 100>.
- This comprises a cathode chamber K K ⁇ 102>, a central chamber K M ⁇ 103> and an anode chamber K A ⁇ 101>.
- the anode chamber K A ⁇ 101> and the central chamber K M ⁇ 103> are separated from one another by an anion exchange membrane extending over the entire cross section of the three-chamber cell E ⁇ 100> as a diffusion barrier D ⁇ 110>.
- the cathode chamber K K ⁇ 102> and the central chamber K M ⁇ 103> are separated from one another by a permeable solid electrolyte (NaSICON) ⁇ 111> which is selective for sodium ions and extends over the entire cross section of the three-chamber cell E ⁇ 100>.
- the cathode chamber K K ⁇ 102> comprises a cathodic electrode E K ⁇ 105>, an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>.
- the anode chamber K A ⁇ 101> comprises an anodic electrode E A ⁇ 104> and a drain A KA ⁇ 106> and is connected to the central chamber K M ⁇ 103> via the connection V AM ⁇ 112>.
- the middle chamber K M ⁇ 103> also includes an inlet Z KM ⁇ 108>.
- the connection V AM ⁇ 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, with which liquid from the central chamber K M ⁇ 103> in the anode chamber K A ⁇ 101> can be conducted outside the outer wall W A ⁇ 117> of the three-chamber cell E ⁇ 100>.
- connection V AM ⁇ 112> connects an outlet A KM ⁇ 118>, which breaks through the outer wall W A ⁇ 117> of the electrolysis cell E ⁇ 100> at the bottom of the central chamber K M ⁇ 103>, with an inlet Z KA ⁇ 119>, which at the bottom of the anode chamber K A ⁇ 101> breaks through the outer wall W A ⁇ 117> of the electrolytic cell E ⁇ 100>.
- An electrolyte L 2 ⁇ 113> is fed into the cathode chamber K K ⁇ 102> via the inlet Z KK ⁇ 107>.
- the electrolyte L 2 ⁇ 113> comprises methanol; a methanolic solution of sodium methoxide L 2 ⁇ 113> is preferably used as the electrolyte L 2 ⁇ 113>.
- an aqueous NaCl solution L 3 ⁇ 114> with a pH of 10.5 is introduced into the central chamber K M ⁇ 103> via the inlet Z KM ⁇ 108>. This flows through the central chamber K M ⁇ 103> and the connection V AM ⁇ 112> into the anode chamber K A ⁇ 101>.
- a voltage is applied between the cathodic electrode E K ⁇ 105> and the anodic electrode E A ⁇ 104>.
- methanol in the electrolyte L 2 ⁇ 113> is reduced to methanolate and H 2 in the cathode chamber K K ⁇ 102> (CH 3 OH + e - ⁇ CH 3 O - + 1 ⁇ 2 H 2 ).
- the oxidation of chloride ions to molecular chlorine takes place (Cl - ⁇ 1 ⁇ 2 Cl 2 + e - ).
- Chlorine gas Cl 2 forms in water according to the reaction Cl 2 + H 2 O ⁇ HOCl + HCl hypochlorous acid and hydrochloric acid, which react acidic with other water molecules.
- the acidity damages the NaSICON solid electrolyte ⁇ 111>, but is affected by the Arrangement in the anode chamber K A ⁇ 101> and thus kept away from the NaSICON solid electrolyte F K ⁇ 111> in the electrolysis cell E ⁇ 100>. This increases its service life considerably.
- the acid-sensitive NaSICON solid electrolyte ⁇ 111> becomes the resulting in the anode chamber K A ⁇ 101> before the increased acidity compared to L 3 ⁇ 114> Solution L 4 ⁇ 116> protected.
- connection V AM ⁇ 112> within the electrolysis cell E ⁇ 100> is designed in such a way that the diffusion barrier D ⁇ 110> does not extend over the entire cross section of the three-chamber cell E ⁇ 100>.
- the connection V AM ⁇ 112> from the central chamber K M ⁇ 103> into the anode chamber K A ⁇ 101> is thereby formed by a gap in the diffusion barrier D ⁇ 110>.
- diffusion barriers D ⁇ 110> with more than one gap can also be used, so that the connection V AM ⁇ 112> between central chamber K M ⁇ 103> and anode chamber K A ⁇ 101> passes through several gaps trains.
- NM Sodium methylate
- the electrolytic cell consisted of three chambers, as in illustration 1 shown, with the anolyte being transferred through the middle chamber into the anode chamber.
- the connection between the central and anode chambers is established by a hose that is attached to the bottom of the electrolysis cell.
- the anode chamber and the middle chamber were separated by a 2.83 cm 2 anion exchange membrane (Tokuyama AMX, ammonium groups on polymer).
- the cathode and central chamber were separated by a ceramic of the NaSICON type with an area of 2.83 cm 2 .
- the ceramic has a chemical composition of the formula Na 3.4 Zr 2.0 Si 2.4 P 0.6 O 12 .
- the flow rate of the anolyte and that of the catholyte were each 90 mL / h, and a current of 0.14 A was applied.
- the temperature was 35 ° C.
- the voltage curve (in V) over time (in hours) is in Figure 3 shown ( ⁇ ).
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EP20165238.5A EP3885470B1 (fr) | 2020-03-24 | 2020-03-24 | Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres |
US17/204,629 US11174559B2 (en) | 2020-03-24 | 2021-03-17 | Process for preparing alkali metal alkoxides in a three-chamber electrolysis cell |
CA3112138A CA3112138C (fr) | 2020-03-24 | 2021-03-18 | Procede de preparation d`alcoolates metalliques alcalins dans une cellule d`electrolyse a trois chambres |
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EP3885471B1 (fr) * | 2020-03-24 | 2023-07-19 | Evonik Operations GmbH | Procédé amélioré de fabrication d'alcools de sodium |
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DE19844059A1 (de) | 1998-09-25 | 2000-03-30 | Degussa | Elektrolysezelle und deren Verwendung |
EP1312700A3 (fr) | 2001-11-02 | 2003-05-28 | Degussa AG | Procédé pour la production d'alcoolats de metaux alcalins |
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Also Published As
Publication number | Publication date |
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EP3885470B1 (fr) | 2023-06-28 |
ES2955404T3 (es) | 2023-11-30 |
CA3112138A1 (fr) | 2021-09-24 |
US11174559B2 (en) | 2021-11-16 |
US20210301409A1 (en) | 2021-09-30 |
CA3112138C (fr) | 2023-03-14 |
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