WO2024083323A1 - Procédé amélioré de dépolymérisation de polyéthylène téréphtalate - Google Patents
Procédé amélioré de dépolymérisation de polyéthylène téréphtalate Download PDFInfo
- Publication number
- WO2024083323A1 WO2024083323A1 PCT/EP2022/079048 EP2022079048W WO2024083323A1 WO 2024083323 A1 WO2024083323 A1 WO 2024083323A1 EP 2022079048 W EP2022079048 W EP 2022079048W WO 2024083323 A1 WO2024083323 A1 WO 2024083323A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- partition wall
- pet
- electrolysis cell
- solution
- chamber
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 109
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 103
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 103
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 88
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims abstract description 51
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 28
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 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 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 239000011591 potassium Substances 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000005192 partition Methods 0.000 claims description 203
- 238000005868 electrolysis reaction Methods 0.000 claims description 128
- 239000000243 solution Substances 0.000 claims description 118
- 239000007784 solid electrolyte Substances 0.000 claims description 70
- 239000000919 ceramic Substances 0.000 claims description 65
- 230000008569 process Effects 0.000 claims description 57
- 238000009792 diffusion process Methods 0.000 claims description 47
- 239000003513 alkali Substances 0.000 claims description 36
- 230000004888 barrier function Effects 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 150000001768 cations Chemical class 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 2
- 150000001463 antimony compounds Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- BCBHDSLDGBIFIX-UHFFFAOYSA-M 4-[(2-hydroxyethoxy)carbonyl]benzoate Chemical compound OCCOC(=O)C1=CC=C(C([O-])=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-M 0.000 abstract description 16
- 238000003776 cleavage reaction Methods 0.000 abstract description 10
- 230000007017 scission Effects 0.000 abstract description 10
- 150000001340 alkali metals Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical compound OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-N 0.000 abstract description 3
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 34
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 24
- 229920003023 plastic Polymers 0.000 description 24
- 239000004033 plastic Substances 0.000 description 24
- 125000003158 alcohol group Chemical group 0.000 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 150000004820 halides Chemical class 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000004744 fabric Substances 0.000 description 10
- 230000005484 gravity Effects 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000047703 Nonion Species 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 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
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000003842 bromide salts Chemical class 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004801 Chlorinated PVC Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 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
- 238000001816 cooling Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010327 methods by industry Methods 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 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
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001568 phenolic resin Polymers 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
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- IXURVUHDDXFYDR-UHFFFAOYSA-N 1-[4-(difluoromethoxy)-3-(oxolan-3-yloxy)phenyl]-3-methylbutan-1-one Chemical compound CC(C)CC(=O)C1=CC=C(OC(F)F)C(OC2COCC2)=C1 IXURVUHDDXFYDR-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- VCIUVNXPUIRTKO-UHFFFAOYSA-N 2-(2-hydroxyethyl)terephthalic acid Chemical compound OCCC1=CC(C(O)=O)=CC=C1C(O)=O VCIUVNXPUIRTKO-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229920001634 Copolyester Polymers 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
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 241001481790 Rupicapra rupicapra Species 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000005553 drilling Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- 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
- C25B13/02—Diaphragms; Spacing elements 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
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- 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
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- PET polyethylene terephthalate
- BHET bis-(2-hydroxyethyl) terephthalate
- MHET mono-(2-hydroxyethyl) terephthalate
- TS terephthalate
- the present invention thus also relates to a process for recycling PET, in which the BHET obtained in the process for depolymerizing PET is polymerized back into PET, optionally after further purification.
- PET Polyethylene terephthalate
- the state of the art proposes several methods for splitting PET.
- GB 784,248 A describes the methanolysis of PET.
- the object of the present invention was to provide such a method.
- the present invention relates to a process for depolymerizing polyethylene terephthalate PET, comprising the following steps:
- step (b) reacting PET in a mixture comprising glycol and at least a portion of the MAOR comprised by Li ⁇ 21> or, if step (a*) is carried out, at least a portion of the MAOR comprised by F* or at least a portion of the MAOR comprised by L-i*, to form bis(2-hydroxyethyl) terephthalate BH ET.
- the present invention relates to a process for recycling PET, in which in a step (Q) the BHET obtained in the depolymerization process according to the invention is polymerized to PET.
- Figure 1 A shows the process according to the invention for producing the sodium methylate solution Li ⁇ 21> in an electrolysis cell E ⁇ 1>. This comprises a cathode chamber KK ⁇ 12> and an anode chamber KA ⁇ 11>.
- the cathode chamber KK ⁇ 12> comprises a cathodic electrode EK ⁇ 123> in the interior IKK ⁇ 122>, an inlet ZKK ⁇ 120> and an outlet A ⁇ 121>.
- the anode chamber KA ⁇ 11> comprises an anodic electrode EA ⁇ 113> in the interior IKA ⁇ 112>, an inlet ZKA ⁇ 110> and an outlet AKA ⁇ 111>.
- the two chambers KA ⁇ 11> and KK ⁇ 12> are delimited by an outer wall WA ⁇ 80> of the two-chamber cell E ⁇ 1>.
- the interior I ⁇ 122> is also separated from the interior IKA ⁇ 112> by a partition ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte ceramic FA ⁇ 18> that is selectively permeable to sodium ions.
- the NaSICON solid electrolyte ceramic FA ⁇ 18> extends over the entire depth and height of the two-chamber cell E ⁇ 1>.
- the partition has two sides SKK ⁇ 161> and SA/MK ⁇ 162>, the surfaces of which OKK ⁇ 163> and OA/MK ⁇ 164> contact the respective interior IKK ⁇ 122> and IKA ⁇ 112>.
- An aqueous solution of sodium chloride L3 ⁇ 23> with pH 10.5 is added against gravity into the interior chamber IKA ⁇ 112> via the inlet ZKA ⁇ 110>.
- a solution of 1 wt.% sodium methylate in methanol L2 ⁇ 22> is fed into the interior chamber IKK ⁇ 122> via the inlet ZKK ⁇ 120>.
- a voltage is applied between the cathodic electrode EK ⁇ 123> and the anodic electrode EA ⁇ 113>.
- methanol in the electrolyte L2 ⁇ 22> in the interior IKK ⁇ 122> is reduced to methylate and H2 (HOCHa + e _ — » CHsO' + 14 H2).
- Sodium ions diffuse from the interior IKA ⁇ 112> through the NaSICON solid electrolyte ceramic FA ⁇ 18> into the interior IKK ⁇ 122>.
- Figure 1 B shows a further embodiment of the method according to the invention using an electrolysis cell E ⁇ 1> which comprises a central chamber KM ⁇ 13>.
- This three-chamber cell E ⁇ 1> accordingly comprises a cathode chamber K ⁇ 12>, an anode chamber A ⁇ 11> and a central chamber KM ⁇ 13> located therebetween.
- the cathode chamber KK ⁇ 12> comprises a cathodic electrode EK ⁇ 123> in the interior IKK ⁇ 122>, an inlet ZKK ⁇ 120> and an outlet A ⁇ 121>.
- the anode chamber KA ⁇ 11> comprises an anodic electrode EA ⁇ 113> in the interior IKA ⁇ 112>, an inlet ZKA ⁇ 110> and an outlet AKA ⁇ 111>.
- the middle chamber K ⁇ 13> comprises an interior chamber I M ⁇ 132>, an inlet Z M ⁇ 130> and an outlet AK ⁇ 131>.
- the interior space IKA ⁇ 112> is connected to the interior space I M ⁇ 132> via the connection VAM ⁇ 15>.
- the three chambers are delimited by an outer wall WA ⁇ 80> of the three-chamber cell E ⁇ 1>.
- the interior IK ⁇ 132> of the middle chamber KM ⁇ 13> is also separated from the interior IKK ⁇ 122> of the cathode chamber KK ⁇ 12> by a partition W ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte ceramic FA ⁇ 18> that is selectively permeable to sodium ions.
- the NaSICON solid electrolyte ceramic FA ⁇ 18> extends over the entire depth and height of the three-chamber cell E ⁇ 1>.
- the partition has two sides SKK ⁇ 161> and SA/ K ⁇ 162>, the surfaces of which OKK ⁇ 163> and OA/MK ⁇ 164> contact the respective interior IKK ⁇ 122> and IKM ⁇ 132>.
- the interior IK ⁇ 132> of the middle chamber KM ⁇ 13> is additionally separated from the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11> by a diffusion barrier D ⁇ 14>.
- the NaSICON solid electrolyte ceramic FA ⁇ 18> and the diffusion barrier D ⁇ 14> extend over the entire depth and height of the three-chamber cell E ⁇ 1>.
- the diffusion barrier D ⁇ 14> is a cation exchange membrane (sulfonated PTFE).
- connection VAM ⁇ 15> is formed outside the electrolysis cell E ⁇ 1>, in particular by a pipe or hose, the material of which can be selected from rubber, metal or plastic.
- liquid can be conducted from the interior IKM ⁇ 132> of the middle chamber KM ⁇ 13> into the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11> outside the outer wall WA ⁇ 80> of the three-chamber cell E ⁇ 1>.
- connection VAM ⁇ 15> connects the outlet AKM ⁇ 131>, which breaks through the outer wall WA ⁇ 80> of the electrolysis cell E ⁇ 1> at the bottom of the middle chamber K ⁇ 13>, with the inlet ZKA ⁇ 110>, which breaks through the outer wall WA ⁇ 80> of the electrolysis cell E ⁇ 1> at the bottom of the anode chamber KA ⁇ 11>.
- An aqueous solution of sodium chloride L3 ⁇ 23> with a pH of 10.5 is fed via the inlet ZKM ⁇ 130> in the same direction as gravity into the interior IKM ⁇ 132> of the middle chamber KM ⁇ 13>.
- the interior IKM ⁇ 132> of the middle chamber M ⁇ 13> is connected to the interior IKA ⁇ 1 12> of the anode chamber KA ⁇ 1 1 > by the connection VAM ⁇ 15>.
- Sodium chloride solution L3 ⁇ 23> is fed from the interior IKM ⁇ 132> into the interior IKM ⁇ 112> by this connection VAM ⁇ 15>.
- a solution of ⁇ 1 wt.% sodium methylate in methanol L2 ⁇ 22> is fed into the interior chamber IKK ⁇ 122> via the inlet ZKK ⁇ 120>.
- a voltage is applied between the cathodic electrode EK ⁇ 123> and the anodic electrode EA ⁇ 113>.
- methanol in the electrolyte L2 ⁇ 22> in the interior IKK ⁇ 122> is reduced to methoxide and H2 (CH3OH + e’ — > CHsO" + 1 H2).
- Sodium ions diffuse from the interior IKM ⁇ 132> of the middle chamber KM ⁇ 103> through the NaSICON solid electrolyte ceramic FA ⁇ 18> into the interior IKK ⁇ 122>.
- the acidity would damage the NaSICON solid electrolyte ceramic FA ⁇ 18>, but is limited to the anode chamber KA ⁇ 11> by the arrangement in the three-chamber cell and thus kept away from the NaSICON solid electrolyte ceramic FA ⁇ 18> in the electrolysis cell E ⁇ 1>. This considerably increases its service life.
- Figure 2 A shows a preferred partition wall W ⁇ 16>.
- This comprises two NaSICON solid electrolyte ceramics FA ⁇ 18> and FB ⁇ 19>, which are separated from each other by a separating element T ⁇ 17> and are each attached to it without gaps.
- the separating element T ⁇ 17> has the geometric shape of a cuboid, on the opposite sides of which FA ⁇ 18> and FB ⁇ 19> are attached without gaps (e.g. by means of adhesive).
- FIG. 2 B shows another embodiment of a preferred partition wall W ⁇ 16>.
- This comprises four NaSICON solid electrolyte ceramics FA ⁇ 18>, FB ⁇ 19>, Fc ⁇ 28>, FD ⁇ 29>, which are separated from one another by a separating element T ⁇ 17> and are each attached thereto without gaps.
- the separating element T ⁇ 17> has the shape of a cross, on the opposite sides of which FA ⁇ 18>, FB ⁇ 19>, Fc ⁇ 28> and FD ⁇ 29> are glued.
- the side SKK ⁇ 161> with the surface OKK ⁇ 163> lies in the image plane
- the side SA/MK ⁇ 162> with the surface OA/MK ⁇ 164> (not visible in Fig. 2 B) lies behind the image plane.
- Figure 3 A shows the detailed view, which is highlighted by a dashed circle in Figures 2 A and 2 B.
- the respective solid electrolyte ceramics FA ⁇ 18> and FB ⁇ 19> are attached to the separating element T ⁇ 17>, for example by means of adhesive.
- Figure 3 B illustrates a further embodiment of a preferred partition wall W.
- the separating element T ⁇ 17> has two concave depressions (grooves) into which the two solid electrolyte ceramics FA ⁇ 18> and FB ⁇ 19> are fitted.
- the shape of the edges of the solid electrolyte ceramics FA ⁇ 18> and FB ⁇ 19> can be mechanically adapted accordingly.
- a seal Di ⁇ 40> is used, which is attached, for example, with an adhesive to the separating element T ⁇ 17> and the respective solid electrolyte ceramic FA ⁇ 18> or FB ⁇ 19>.
- the separating element T ⁇ 17> can consist of two or more parts ⁇ 171> and ⁇ 172>, which can be attached to one another, as indicated by the dashed line in Fig. 3 B.
- the latter can be clamped between the two parts ⁇ 171> and ⁇ 172>, which further improves the stability of the connection separating element T ⁇ 17> / ceramic FA ⁇ 18> or FB ⁇ 19> and the tightness of the partition wall W ⁇ 16>.
- Figure 3 C illustrates a further embodiment of a preferred partition wall W. This corresponds to that described in Figure 3 B, except that the recesses (grooves) in the separating element T ⁇ 17>, into which the two solid electrolyte ceramics FA ⁇ 18> and FB ⁇ 19> are fitted, are not concave but tapered.
- the partition wall W ⁇ 16> shown in Figure 4 A corresponds to the partition wall W ⁇ 16> shown in Figure 2 A, except that it also includes a frame element R ⁇ 20>. This completely covers all surfaces of the partition wall W ⁇ 16> except OKK ⁇ 163> and OA/ K ⁇ 164>.
- the frame element R ⁇ 20> is not made in one piece with the separating element T ⁇ 17>.
- Figure 4 B shows a further embodiment of a preferred partition wall W ⁇ 16>. This corresponds to the embodiment shown in Figure 4 A, except that it comprises two frame elements R ⁇ 20> which delimit the upper and lower surfaces of the partition wall W ⁇ 16>.
- Figure 4 C shows a further embodiment of a preferred partition wall ⁇ 16>.
- the partition wall W ⁇ 16> shown in Figure 4 C corresponds to the partition wall ⁇ 16> shown in Figure 2 B, except that it also includes a frame element R ⁇ 20>. This completely covers all surfaces of the partition wall W ⁇ 16> except OKK ⁇ 163> and OA/MK ⁇ 164>.
- the frame element R ⁇ 20> is not made in one piece with the partition element T ⁇ 17>.
- Figure 4 D shows a further embodiment of a preferred partition wall ⁇ 16>. This corresponds to the embodiment shown in Figure 4 C, except that it comprises two frame elements R ⁇ 20> which delimit the upper and lower surfaces of the partition wall W ⁇ 16>.
- Figure 5 A shows an electrolysis cell E ⁇ 1> in a preferred embodiment of the method according to the invention. This corresponds to the electrolysis cell shown in Figure 1 A with the difference that a partition W ⁇ 16> separates the interior IKK ⁇ 1 2> of the cathode chamber KK ⁇ 12> from the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11>.
- the partition is the one shown in Figures 2 A and 2 B.
- Figure 5 B shows an electrolysis cell E ⁇ 1> in a preferred embodiment of the method according to the invention. This corresponds to the electrolysis cell shown in Figure 1 A with the difference that a partition W ⁇ 16> separates the interior IKK ⁇ 122> of the cathode chamber KK ⁇ 12> from the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11>.
- the partition W ⁇ 16> is the one shown in Figures 4 A to 4 D.
- the frame element R ⁇ 20> forms part of the outer wall WA ⁇ 80>, SO that the solid electrolyte ceramics enclosed by the partition W ⁇ 16> are protected from the pressure which would act on them through the partition W ⁇ 16> if they were part of the partition W ⁇ 16>.
- the solid electrolyte ceramics are used to completely separate the interior spaces IKK ⁇ 122> and IKA ⁇ 112> within the electrolysis cell E ⁇ 1>, since they are not partially covered by the outer wall.
- Figure 6 A shows the method according to the invention using an electrolysis cell E ⁇ 1> which corresponds to that shown in Fig. 1 B with the difference that the connection VA ⁇ 15> from the interior IKM ⁇ 132> of the middle chamber KM ⁇ 13> to the interior IKA ⁇ 112> of the anode chamber A ⁇ 11> is formed by several perforations in the diffusion barrier D ⁇ 14>. These perforations can be subsequently punched into the diffusion barrier D ⁇ 14> or can be present in the diffusion barrier D ⁇ 14> from the outset due to the manufacturing process (e.g. in the case of textile fabrics such as filter cloths or metal fabrics). In this embodiment, the totality of these perforations represents the connection VAM ⁇ 15> through which electrolyte can be conducted from the interior IKM ⁇ 132> into the interior IKA ⁇ 112>.
- Figure 6 B shows a further embodiment of the method according to the invention using an electrolysis cell E ⁇ 1>.
- This corresponds to the electrolysis cell E ⁇ 1> shown in Figure 1 B with the difference that the connection VAM ⁇ 15> from the interior IK ⁇ 132> of the middle chamber KM ⁇ 13> to the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11> is formed by a gap which forms between the diffusion barrier D ⁇ 14> and the outer wall A ⁇ 80>.
- This gap can be created by arranging an otherwise tight diffusion barrier D ⁇ 14> in the electrolysis cell E ⁇ 1> in such a way that it does not completely separate the interior IK ⁇ 132> of the middle chamber KM ⁇ 13> from the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11>, but rather a gap is retained as the connection VAM ⁇ 15>.
- Figure 7 A shows a further embodiment of a preferred partition wall W ⁇ 16>.
- This comprises four NaSICON solid electrolyte ceramics FA ⁇ 18>, FB ⁇ 19>, Fc ⁇ 28> and FD ⁇ 29>, which are separated from one another by a separating element T ⁇ 17>, which comprises two halves ⁇ 171> and ⁇ 172>.
- the partition wall W ⁇ 16> also comprises a frame element R ⁇ 20>, which also consists of two halves ⁇ 201> and ⁇ 202>.
- the partition wall W ⁇ 16> consists of two collapsible parts, in which half ⁇ 171> of the partition element T ⁇ 17> is integral with half ⁇ 201> of the frame element R ⁇ 20> and half ⁇ 172> of the partition element T ⁇ 17> is integral with half ⁇ 202> of the frame element R ⁇ 20>. These two parts can optionally be connected to one another via a hinge ⁇ 50> and locked in the folded state via the lock ⁇ 60>.
- the four NaSICON solid electrolyte ceramics FA ⁇ 18>, FB ⁇ 19>, Fc ⁇ 28> and FD ⁇ 29> are clamped between these halves, with a ring acting as a seal Di ⁇ 40> being used for sealing.
- Figure 7 A shows the front view of the SKK ⁇ 161> side with the OKK ⁇ 163> surface of the partition W ⁇ 16>.
- the rings acting as seal Di ⁇ 40> are indicated with dashed outlines.
- the right side of the figure shows the side view of the partition ⁇ 16>.
- Figure 7 B shows a further embodiment of a preferred partition wall W ⁇ 16>. This corresponds to the embodiment described in Figure 7 A, except that it comprises nine NaSICON solid electrolyte ceramics FA ⁇ 18>, FB ⁇ 19>, Fc ⁇ 28>, FD ⁇ 29>, FE ⁇ 30>, FF ⁇ 31>, FG ⁇ 32>, FH ⁇ 33>, Fi ⁇ 34>.
- the solution Li comprising ROH and MAOR used in the process according to the invention is obtained electrolytically in an electrolysis cell E ⁇ 1>.
- glycol means 1,2-ethylenediol with the chemical formula HO-CH2-CH2-OH (CAS No. 107-21-1).
- alkyl radical having 1 to 6 carbon atoms is according to the invention in particular selected from the group consisting of methyl, ethyl, n-propyl, feo-propyl, n-butyl, sec-butyl, /so-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbuty
- 1.2.2-Trimethylpropyl 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, preferably selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, sec-butyl, /so-butyl, tert-butyl, n-pentyl, n-hexyl, even more preferably selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, n-pentyl, n-hexyl.
- an alkyl radical having 1 to 5 carbon atoms is in particular selected from the group consisting of methyl, ethyl, n-propyl, /iso-propyl, n-butyl, sec-butyl, /'iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl,
- 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl preferably selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, sec-butyl, /so-butyl, tert-butyl, n-pentyl, even more preferably selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, n-pentyl.
- an alkyl radical having 1 to 4 carbon atoms is in particular selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, sec-butyl, /so-butyl, tert-butyl, preferably selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, tert-butyl, even more preferably selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl.
- an alkyl radical having 1 to 3 carbon atoms is in particular selected from the group consisting of methyl, ethyl, n-propyl, /so-propyl, preferably selected from the group consisting of methyl, ethyl, /so-propyl.
- MA is an alkali metal cation, in particular selected from lithium, sodium, potassium, and preferably selected from sodium, potassium. Most preferably the alkali metal cation is sodium.
- the solution Li ⁇ 21> of AOR in ROH used in step (b) or in the optional step (a*) of the process according to the invention is prepared in an electrolysis cell E in step (a) of the process according to the invention.
- the electrolysis cell E comprises at least one anode chamber KA and at least one cathode chamber KK and optionally at least one middle chamber KM in between.
- This also includes electrolysis cells E which have more than one anode chamber KA and/or cathode chamber KK and/or middle chamber KM.
- electrolysis cells in which these chambers are joined together in a modular manner are described, for example, in DD 258 143 A3 and US 2006/0226022 A1.
- the electrolysis cell E comprises an anode chamber KA and a cathode chamber KK and optionally a middle chamber K located therebetween.
- the electrolysis cell E usually has an outer wall WA.
- the outer wall WA is made in particular of a material selected from the group consisting of steel, preferably rubberized steel, plastic, which is selected in particular from Telene ® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride).
- A can be perforated in particular for inlets and outlets.
- Within WA there are then at least one anode chamber KA, at least one cathode chamber KK and, in the embodiments in which the electrolysis cell E comprises such a chamber, at least one middle chamber KM in between.
- the at least one cathode chamber KK has at least one inlet ZKK, at least one outlet AKK and an interior space IKK which comprises a cathodic electrode EK.
- the interior space IKA of the anode chamber KA is separated from the interior space IKK of the cathode chamber KK by a partition wall W if the electrolysis cell E does not comprise a middle chamber KM.
- the interior space IKK of the cathode chamber KK is separated from the interior space IKM of the middle chamber K by a partition wall W if the electrolysis cell E comprises at least one middle chamber KM.
- the cathodic chamber KK comprises an interior space IKK, which in turn comprises a cathodic electrode EK.
- a cathodic electrode EK Any electrode familiar to the person skilled in the art that is stable under the conditions of step (a) of the method according to the invention can be used as such a cathodic electrode EK.
- Such electrodes are described in particular in WO 2014/008410 A1, paragraph [025] or DE 10360758 A1, paragraph [030].
- This electrode EK can be selected from the group consisting of knitted wool, three-dimensional matrix structure or “spheres”.
- the cathodic electrode EK comprises in particular a material which is selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, carbon-supported palladium, titanium, more preferably selected from the group consisting of steel, nickel.
- VA steel stainless steel
- the cathode chamber K also comprises at least one inlet ZKK and at least one outlet AKK. This makes it possible to add liquid, such as solution L2, to the interior IKK of the cathode chamber KK and to remove liquid contained therein, such as solution Li.
- the inlet ZKK and the outlet AKK are attached to the cathode chamber KK in such a way that the liquid contacts the cathodic electrode E K as it flows through the interior IKK of the cathode chamber KK.
- step (a) of the method according to the invention is carried out, when the solution L2 of alcohol ROH, which optionally also comprises an alkali metal alcoholate MAOR, is passed through the interior IKK of the cathode chamber KK.
- the inlet ZKK and the outlet AKK can be attached to the electrolysis cell E using methods known to those skilled in the art, e.g. by drilling holes in the outer wall and corresponding connections (valves) that simplify the inlet and outlet of liquid.
- the at least one anode chamber KA has at least one inlet ZKA, at least one outlet AKA and an interior space IKA, which comprises an anodic electrode EA.
- the electrolysis cell E comprises a middle chamber KM
- the interior space IKA of the anode chamber KA is separated from the interior space IKM of the middle chamber KM by a diffusion barrier D.
- the electrolysis cell E does not include a central chamber KM, the interior space IKA of the anode chamber K is separated from the interior space IKK of the cathode chamber KK by the partition wall.
- the anode chamber KA comprises an interior space IKA, which in turn comprises an anodic electrode EA.
- Any electrode familiar to the person skilled in the art that is stable under the conditions of step (a) of the method according to the invention can be used as such anodic electrode EA.
- Such electrodes are described in particular in WO 2014/008410 A1, paragraph [024] or DE 10360758 A1, paragraph [031].
- This electrode EA can consist of one layer or of several flat, parallel layers, each of which can be perforated or expanded.
- the anodic electrode EA comprises in particular a material that is selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, Nickel titanate, precious metals such as platinum in particular, 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).
- Other possible anode materials are in particular stainless steel, lead, graphite, tungsten carbide, titanium diboride.
- the anodic electrode EA preferably comprises a titanium anode coated with ruthenium oxide/iridium oxide (RuCh + I rOz / Ti).
- the anode chamber KA also comprises an inlet ZKA and an outlet AKA.
- the inlet ZKA and the outlet AKA are attached to the anode chamber KA in such a way that the liquid contacts the anodic electrode EA as it flows through the interior IKA of the anode chamber KA. This is the prerequisite for the solution L4 to be obtained at the outlet AKA when step (a) of the method according to the invention is carried out when the solution L3 of a salt S is passed through the interior IKA of the anode chamber KA.
- the inlet ZKA and the outlet AKA can be attached to the electrolysis cell E using methods known to those skilled in the art, e.g. through holes in the outer wall and corresponding connections (valves) that simplify the introduction and discharge of liquid.
- the inlet ZKA can also be located inside the electrolysis cell, for example as a perforation in the diffusion barrier D.
- the electrolysis cell E used in step (a) of the process according to the invention optionally has at least one central chamber KM.
- the optional central chamber KM is located between the cathode chamber KK and the anode chamber KA. It comprises at least one inlet ZKM, at least one outlet AKM and an interior space IKM-
- the electrolysis cell E includes a middle chamber KM
- the interior space IKA of the anode chamber KA is separated from the interior space IKM of the middle chamber KM by a diffusion barrier D.
- AKM is then also connected to the inlet ZKA by a connection VAM, so that liquid from IKM can be fed into IKA via the connection VA.
- the interior space IKM of the optional middle chamber KM is separated from the interior space IKA of the anode chamber KA by a diffusion barrier D and from the interior space IKK of the cathode chamber K by the partition wall W.
- step (a) of the process according to the invention Any material which is stable under the conditions of step (a) of the process according to the invention and which prevents or slows down the transfer of protons from the liquid in the interior space IKA of the anode chamber A into the interior space IKM of the optional middle chamber KM can be used for the diffusion barrier D.
- a non-ion-specific partition 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 wall.
- the material of the non-ion-specific partition wall 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, ceramic, in particular ceramic frits, membrane diaphragm, and is 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 permeable to specific ions"
- this refers to membranes that promote the diffusion of ions of a certain charge type compared to oppositely charged ions.
- membranes permeable to specific ions also promote the diffusion of certain ions with one charge type compared to other ions of the same charge type through them.
- 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 certain anions. In other words, they promote the diffusion of anions through them over that of cations, in particular over protons, and even more preferably they additionally promote 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 conduct certain cations. In other words, they favor the diffusion of cations through them over that of anions, even more preferably they additionally favor the diffusion of certain cations through them over the diffusion of other cations through them, even more preferably of cations which are not protons, even more preferably sodium cations, over protons.
- “Favour 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 higher by a factor of 10, preferably 100, preferably 1000 than the diffusion coefficient of the ion type Y for the membrane in question.
- the diffusion barrier D is a “membrane permeable to specific ions”, it is preferably an anion-conducting membrane, because this is particularly effective at preventing the diffusion of protons from the anode chamber KA into the middle chamber KM.
- the anion-conducting membrane used is in particular one that is selective for the anions comprised by the salt S.
- Such membranes are known to the person skilled in the art and can be used by him.
- the salt S comprises MA as a cation.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, hydrogen carbonate or carbonate of MA, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- the anion-conducting membrane used is a membrane that is selective for halides, preferably chloride.
- the diffusion barrier D is a cation-conducting membrane, it is in particular a membrane which is selective for MA, i.e. the cation comprised by the salt S. Even more preferably, the diffusion barrier D is an alkali cation-conducting membrane, even more preferably a potassium and/or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.
- 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 cation-conducting membranes, wherein these carry covalently bound functional groups selected from -SO 3 -, -COO', -PO 3 2 -, -PO 2 H-, preferably -SOs', (described in DE 10 2010 062 804 A1, US 4,831,146).
- Neosepta® membranes are described, for example, by S.A. Mareev, D.Yu. Butylskii, N.D. Pismenskaya, C. Larchet, L. Dammak, V.V. Nikonenko, Journal of Membrane Science 2018, 563, 768-776.
- a cation-conducting membrane is used as diffusion barrier D, this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula PNAFION, where n and m are independently an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , even more preferably an integer from 10 2 to 10 4 .
- the optional middle chamber K M also includes an inlet ZKM and an outlet AKM. This makes it possible to add liquid, such as solution L3, to the interior IKM of the middle chamber KM and to transfer liquid contained therein, such as solution L3, to the interior IKA of the anode chamber KA ZU.
- the inlet ZK and the outlet AKM can be attached to the electrolysis cell E using methods known to those skilled in the art, e.g. through holes in the outer wall and corresponding connections (valves) that simplify the inflow and outflow of liquid.
- the outlet AK can also be located inside the electrolysis cell, for example as a perforation in the diffusion barrier D.
- the outlet AK is connected to the inlet ZKA SO by a connection VAM, so that liquid from IKM can be passed into IKA through the connection VA.
- connection VA can be formed within the electrolysis cell E and/or outside the electrolysis cell E, and is preferably formed within the electrolysis cell.
- connection VA is formed within the electrolysis cell E, it is preferably formed by at least one perforation in the diffusion barrier D.
- This embodiment is particularly preferred when a non-ion-specific partition wall, in particular a metal mesh or textile fabric, is used as the diffusion barrier D.
- connection VAM is formed outside the electrolysis cell E, wherein it is preferably formed by a connection of AKM and ZKA running outside the electrolysis cell E, in particular by forming an outlet AK from the interior IKM of the middle chamber KM through the outer wall WA, preferably at the bottom of the middle chamber M, wherein even more preferably the inlet ZK is at the top of the middle chamber K, and an inlet ZKA into the interior IKA of the anode chamber KA is formed through the outer wall WA, preferably at the bottom of the anode chamber KA, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
- the outlet AKA is then even more preferably formed at the top of the anode chamber KA.
- Outlet AK at the bottom of the middle chamber K means that the outlet AKM SO is attached to the electrolysis cell E so that the solution L 3 leaves the middle chamber KM in the same direction as gravity.
- Inlet ZKA at the bottom of the anode chamber KA means that the inlet ZKA SO is attached to the electrolysis cell E so that the solution L 3 enters the anode chamber KA against gravity.
- Inlet ZK at the top of the middle chamber KM means that the inlet ZKM SO is attached to the electrolysis cell E so that the solution L 3 enters the middle chamber KM in the same direction as gravity.
- Drain AKA at the top of the anode chamber KA means that the drain AKA SO is attached to the electrolysis cell E so that the solution L4 leaves the anode chamber KA against gravity.
- connection VAM is formed outside the electrolysis cell E, in particular ZKM and AKM are arranged on opposite sides of the outer wall WA of the middle chamber KM (i.e. ZKM at the bottom and AKM at the top of the electrolysis cell E or vice versa) and ZKA and AKA are arranged on opposite sides of the outer wall WA of the anode chamber KA (i.e. ZKA at the bottom and AKA at the top of the electrolysis cell E or vice versa), as shown in particular in Figure 1 B. Due to this geometry, L 3 must connect the two chambers KM and A flow through. ZKA and ZKM can be formed on the same side of the electrolysis cell E, in which case AKM and AKA are also automatically formed on the same side of the electrolysis cell E. Alternatively, ZKA and ZKM can be formed on opposite sides of the electrolysis cell E, as in the embodiment shown in Figure 1 B, in which case AKM and AKA are also automatically formed on opposite sides of the electrolysis cell E.
- connection VAM is formed within the electrolysis cell E, this can be ensured in particular by one side (“side A”) of the electrolysis cell E, which is the top or bottom of the electrolysis cell E, preferably the top as shown in Figure 6 B, comprising the inlet ZKM and the outlet AKA and the diffusion barrier D extending from this side (“side A”) into the electrolysis cell E, but not quite reaching the side (“side B”) of the electrolysis cell E opposite side A, which is then the bottom or top of the electrolysis cell E, and spanning 50% or more of the height of the three-chamber cell E, more preferably 60% to 99% of the height of the three-chamber cell E, even more preferably 70% to 95% of the height of the three-chamber cell E, even more preferably 80% to 90% of the height of the three-chamber cell E, even more preferably 85% of the height of the three-chamber cell E.
- bottom of the electrolysis cell E is the side of the electrolysis cell E through which a solution (e.g. L3 for AKM in Figure 1 B) 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. L2 for ZKK in Figures 1 A, 1 B, 5 A, 5 B, 6 A and 6 B and L3 for ZKA in Figures 1 A, 1 B, 5 A and 5 B) is fed to the electrolysis cell E against gravity.
- a solution e.g. L3 for AKM in Figure 1 B
- a solution e.g. L2 for ZKK in Figures 1 A, 1 B, 5 A, 5 B, 6 A and 6 B and L3 for ZKA in Figures 1 A, 1 B, 5 A and 5 B
- top of the electrolysis cell E is the side of the electrolysis cell E through which a solution (eg L4 for AKA and Li for AKK in Figures 1 A, 1 B, 5 A, 5 B, 6 A and 6 B) exits the electrolysis cell E against gravity or the side of the electrolysis cell E through which a solution (eg L3 for ZKM in Figures 1 B, 6 A and 6 B) is fed to the electrolysis cell E in the same direction as gravity.
- a solution eg L4 for AKA and Li for AKK in Figures 1 A, 1 B, 5 A, 5 B, 6 A and 6 B
- a solution eg L3 for ZKM in Figures 1 B, 6 A and 6 B
- the interior IKM also comprises at least one additional feature selected from:
- an additional introduction of an inert gas e.g. nitrogen or noble gas
- an inert gas e.g. nitrogen or noble gas
- the electrolysis cell E used in step (a) of the process according to the invention comprises a partition wall W.
- the partition wall W comprises at least one alkali cation-conducting solid electrolyte ceramic FA.
- the partition wall W consists of an alkali cation-conducting solid electrolyte ceramic FA.
- the partition wall W comprises at least two alkali cation-conducting solid electrolyte ceramics (“alkali cation-conducting solid electrolyte ceramic” is abbreviated to “AFK” below) FA and FB, optionally separated from one another by a separating element T.
- alkali cation-conducting solid electrolyte ceramic is abbreviated to “AFK” below
- FA and FB optionally separated from one another by a separating element T.
- the partition W has two sides SKK and SA/K which are opposite each other, that is to say the side SA/MK is opposite the side SKK (and vice versa).
- the two sides SKK and SA/K comprise planes which are substantially parallel to each other.
- the geometry of the partition wall W is otherwise not further restricted and can be adapted in particular to the cross-section of the electrolysis cell E in which it is used.
- it can have the geometry of a cuboid and thus have a rectangular cross-section, or the geometry of a truncated cone or cylinder and thus have a circular cross-section.
- the partition wall W can also have the geometry of a cuboid with rounded corners and/or bulges, which in turn can have holes.
- the partition wall W then has bulges (“rabbit ears”) with which the partition wall W can be fixed to electrolysis cells or frame parts of the partition wall W can be fixed to each other.
- the side SKK of the partition W has the surface OKK and the side SA/MK of the partition W has the surface OA/K.
- partition wall means that the partition wall W is liquid-tight. Thus, there are no gaps through which aqueous solution, alcoholic solution, alcohol or water could flow from the SKK side to the SA/MK side or vice versa.
- the partition wall W comprises at least two alkali cation-conducting solid electrolyte ceramics F ⁇ and F B and optionally a separating element T, this means that FA and FB and the optionally present at least one separating element T are connected to one another without gaps.
- the partition wall W which can be used in the electrolysis cell E according to step (a) of the method according to the invention also includes embodiments in which the partition wall W comprises more than two AFKs, e.g. four or nine or twelve AFKs, wherein the AFKs either directly adjoin one another or are separated from one another by a separating element T.
- the partition wall W comprises more than two AFKs, e.g. four or nine or twelve AFKs, wherein the AFKs either directly adjoin one another or are separated from one another by a separating element T.
- the partition wall W comprises more than one AFK, all AFKs enclosed by the partition wall W are separated from one another by at least one separating element T in the partition wall W, i.e. no AFK is directly connected to another AFK, i.e. without a separating element T in between.
- the partition wall W is further characterized in that the AFK FA enclosed by the partition wall W can be directly contacted both via the OKK surface and via the OA/K surface.
- the partition wall W comprises at least two AFKs FA, F B , it is preferred that all AFKs enclosed by the partition wall W can be directly contacted both via the OKK surface and via the OA/MK surface.
- Directly contactable means, with reference to the AFKs enclosed by the partition wall W, that at least part of the surfaces OKK and OA/K is formed by the surface of the AFKs enclosed by the partition wall W, i.e. that the AFKs enclosed by the partition wall W are directly accessible at the two surfaces OKK and OA/MK, so that they can be wetted at the two surfaces OKK and OA/MK, for example with aqueous solution, alcoholic solution, alcohol ROH or water.
- the at least one separating element T can typically also be directly contacted via at least a part of the surface OKK as well as via at least a part of the surface OA/MK.
- Directly contactable means, with reference to the at least one separating element T optionally included by the partition W, that a part of the surfaces OKK and OA/K is formed by the surface of the separating element T, i.e. that the separating element T is directly accessible at the two surfaces OKK and OA/MK, so that the separating element T can be wetted at the two surfaces OKK and OA/MK, for example with aqueous solution, alcoholic solution, alcohol or water.
- the partition wall W at least 50%, more preferably at least 60%, even more preferably at least 70%, even more preferably at least 85% of the surface OA/MK is formed by the AFKs encompassed by the partition wall W.
- the partition wall W at least 50%, more preferably at least 60%, even more preferably at least 70%, even more preferably at least 85% of the surface OKK is formed by the AFKs encompassed by the partition wall W.
- the partition wall W has more than one AFK, in particular 50% to 99%, more preferably 60% to 96%, even more preferably 70% to 92%, even more preferably 85% to 90% of the surface OKK is formed by the AFKs encompassed by the partition wall W, with even more preferably the remainder of the surface OKK being formed by the partition element T and optionally the frame element R.
- the partition wall W has more than one AFK, in particular 50% to 99%, more preferably 60% to 96%, even more preferably 70% to 92%, even more preferably 85% to 90% of the surface OA/K is formed by the AFKs encompassed by the partition wall W, with even more preferably the remainder of the surface OA/MK being formed by the partition element T and optionally the frame element R.
- the partition wall W ⁇ 16> comprises an alkali cation-conducting solid electrolyte ceramic FA and optionally a frame element R. Even more preferably, the partition wall W ⁇ 16> consists of an alkali cation-conducting solid electrolyte ceramic FA.
- the partition W comprises at least four AFKs FA, FB, FC and FD, and then more preferably comprises exactly four AFKs FA, FB, Fc and FD.
- the partition W comprises at least nine AFKs FA, FB, FC, FD, FE, FF, FG, FH and F
- the partition W comprises at least twelve AFKs FA, FB, FC, FD, FE, FF, FG, FH, FI, FJ, FK and FL, and then more preferably it comprises exactly twelve AFKs FA, FB, FC, FD, FE, FF, FG, FH, FI, FJ, FK and FL.
- the arrangement of at least two AFKs next to each other in the partition wall W has an advantage over the arrangement of just one AFK, namely a further direction of propagation for the AFKs in the event of temperature fluctuations that occur during operation of the electrolysis cell.
- NaSICON discs which act as partition walls, are delimited in electrolysis cells by the outer walls of the electrolysis cell or by solid plastic frames. The mechanical stresses that occur within the NaSICON during expansion cannot therefore be dissipated, which can lead to the ceramic breaking.
- each AFK has at least one further degree of freedom available, i.e. a dimension in which it can expand.
- expansion in the z direction i.e. across the thickness of the ceramic disk at right angles to the plane of the partition W
- expansion in the x and/or y direction is now also possible, i.e. in the horizontal and vertical direction within the plane of the partition W.
- AFKs for example, span the cross-section of the electrolysis cell as a solid disk and border on the solid wall of the electrolysis cell; compared to a partition of the same size that only consists of one AFK, the division into several small AFKs results in the stresses that occur within the smaller AFKs also being absolutely smaller, can be dissipated more quickly and This means that tension cannot build up so quickly that it would cause the AFK to break.
- any solid electrolyte through which cations, in particular alkali cations, even more preferably sodium cations, can be transported from the SA/MK side to the SKK side can be considered as alkali cation-conducting solid electrolyte ceramics FA, FB etc. enclosed by the partition wall.
- Such solid electrolytes are known to the person skilled in the art and are described, for example, in DE 10 2015 013 155 A1, in WO 2012/048032 A2, paragraphs [0035], [0039], [0040], in US 2010/0044242 A1, paragraphs [0040], [0041], in DE 10360758 A1, paragraphs [014] to [025]. They are sold commercially under the names NaSICON, LiSICON, KSICON.
- a sodium ion-conducting solid electrolyte is preferred, and even more preferably it has a NaSICON structure.
- NaSICON structures that can be used according to the invention are also described, for example, by N. Anantharamulu, K. Koteswara Rao, G. Rambabu, B. Vijaya Kumar, Velchuri Radha, M. Vithal, J Mater Sei 2011 , 46, 2821-2837.
- the alkali cation-conducting solid electrolyte ceramics encompassed by the partition wall W, and in particular the AFK FA, independently of one another have a NaSICON structure of the formula M'i+2w+x-y+z M H W M IH x ZH wxy M v y (SiO4)z (PO4)3-z.
- M 1 is selected from Na + , Li + , preferably Na + .
- M 11 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 111 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 w, x, y, z are chosen such that 1 + 2w + x - y + z > 0 and 2 - w - x - y > 0.
- partition wall W in which it comprises at least two AFKs FA, FB, all AFKs encompassed by the partition wall W have the same structure.
- the partition wall W preferably comprises a separating element T.
- the separating element T then separates according to the invention at least two alkali cation-conducting solid electrolyte ceramics FA and FB encompassed by the partition wall W, that is to say it is arranged between at least two alkali cation-conducting solid electrolyte ceramics FA and FB encompassed by the partition wall.
- any body by which the respective AFKs can be arranged separately from one another is suitable as the separating element T, which is preferably enclosed by the separating wall W.
- the AFKs are connected seamlessly to the separating element T in order not to impair the function of the separating wall, which is intended to separate the cathode chamber in the electrolysis cell E from the adjacent middle or anode chamber in a liquid-tight manner.
- the shape of the partition element T can be selected by the person skilled in the art depending on the number of AFKs that the partition wall comprises in the preferred embodiment.
- the partition wall comprises, for example, two or three AFKs, these can each be separated by a web arranged between the AFKs as a separating element T.
- the partition wall comprises four or more AFKs, these can be separated by a dividing element T, which has the shape of a cross or grid.
- the partition wall W comprises at least two AFKs FA, FB, it is particularly preferred that the partition wall W comprises at least four AFKs and even more preferably that the separating element T is then cross-shaped or grid-shaped, since it is then ensured that all three dimensions are completely available to the AFKs for thermal expansion/shrinkage.
- the separating element T can consist of one piece.
- the AFK is then attached to the separating element T without gaps, for example using a means known to those skilled in the art, for example using an adhesive, with epoxy resins or phenolic resins preferably being used.
- the separating element T can also be shaped in such a way that the respective AFK fits into the Separating element can be fitted or clamped in. This can be done during the manufacture of the partition wall W.
- the partition wall W comprises a separating element
- it comprises a seal Di ( Figures 3 B, 3 C) in particular between the separating element T and the AFKs. This ensures particularly well that the partition wall W is liquid-tight.
- the seal Di can be selected by the person skilled in the art for the respective AFK or the respective separating element T.
- the seal Di comprises in particular a material which is selected from the group consisting of elastomers, adhesives, preferably elastomers.
- Rubber in particular comes into consideration as an elastomer, preferably ethylene-propylene-diene rubber (“EPDM”), fluoropolymer rubber (“FPM”), perfluoropolymer rubber (“FFPM”), acrylonitrile-butadiene rubber (“NBR”).
- EPDM ethylene-propylene-diene rubber
- FPM fluoropolymer rubber
- FFPM perfluoropolymer rubber
- NBR acrylonitrile-butadiene rubber
- the separating element T comprises at least two parts Ti and T2, which can be fastened to one another and thus clamp the AFKs between them.
- the separating element T preferably comprises a material selected from the group consisting of plastic, glass, wood.
- the separating element T is particularly preferably made of plastic.
- the plastic is one selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, post-chlorinated polyvinyl chloride (“PVC-C”).
- the partition wall W also comprises a frame element R.
- the frame element R differs from the partition element T in that it is not arranged between the alkali cation-conducting solid electrolyte ceramics enclosed by the partition wall W, i.e. it does not separate them from one another.
- the frame element R delimits in particular the surfaces OKK and OA/MK at least partially, preferably completely. This means in particular:
- the frame element R encloses the surfaces OKK and OA/MK at least partially, preferably completely.
- the frame element R may or may not be formed as part of the surfaces OKK and OA/MK.
- the frame element R is preferably formed as part of the surfaces OKK and OA/MK.
- the frame element R can be directly contacted, or not directly contacted, preferably directly contacted, in particular via the OKK and OA/MK surfaces.
- “not directly contactable” means that the frame element R is formed exclusively as at least part of the surfaces of those sides of the partition wall that are not the sides SKK and SA/K.
- the frame element R then forms at least 1%, more preferably at least 25%, more preferably at least 50%, even more preferably 100% of the surfaces of the sides of the partition wall that are not the sides SKK and SA/MK.
- Directly contactable means, with reference to the frame element R optionally enclosed by the partition wall W, that part of the surfaces OKK and OA/MK is formed by the surface of the frame element R, i.e. that the frame element R enclosed by the partition wall W is directly accessible at the two surfaces OKK and OA/K, so that it can be wetted at the two surfaces OKK and OA/MK, for example with aqueous solution, alcoholic solution, alcohol or water.
- the frame element R can also be designed as at least part of the surfaces of those sides of the partition wall W which are not the sides SKK and SA/MK.
- the frame element R forms at least 1%, more preferably at least 25%, more preferably at least 50%, even more preferably 100% of the surfaces of the sides of the partition wall W which are not the sides SKK and SA/MK.
- Fig. 4 B and Fig. 4 D for example, embodiments are shown in which the frame element R forms part of the surfaces of those sides of the partition wall W which are not the sides SKK and SA/MK.
- Fig. 4 A and Fig. 4 C for example, embodiments are shown in which the frame element R completely forms the surfaces of those sides of the partition wall W which are not the sides SKK and SA/MK.
- the frame element R is in particular made of a material which is selected from the group consisting of plastic, glass, wood.
- the frame element R is particularly preferably made of plastic.
- the plastic is one selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, PVC-C.
- the partition W comprises a partition element T and a frame element R
- the frame element R and the partition element T are made of the same material, more preferably both are made of plastic, which is even more preferably selected from polypropylene, polystyrene, polyvinyl chloride, PVC-C.
- the frame element R can consist of one piece.
- the AFK is then attached seamlessly to the frame element R using a means known to those skilled in the art, for example using an adhesive, for which epoxy resins and phenolic resins are particularly suitable.
- the frame element R can also be shaped in such a way that the respective AFK can be fitted or clamped into the frame element R.
- the partition wall W comprises at least two AFKs FA, FB, at least one separating element T and one frame element R, the AFKs, the at least one separating element T and the frame element R adjoin one another without gaps.
- the partition wall W comprises at least two AFKs FA, FB, a frame element R and at least one partition element T, and the frame element R and the at least one partition element T are at least partially formed in one piece
- the frame element R can consist of at least two parts that are fastened to one another and clamp the AFKs between them.
- the partition wall W can then have a hinge on which the two parts of the frame element R can be opened and closed.
- the partition wall W can then have a lock to which the two parts of the frame element R can be locked in the closed position ( Figure 7 A).
- the separating element T In the closed state, the AFKs and, if this is not already formed in one piece with the frame element R, the separating element T can be clamped between the frame element R. In this embodiment, a seal can then be attached between the separating element T and AFK or between the frame element R and AFK in order to ensure liquid tightness.
- the partition wall W comprises at least two AFKs FA, FB, a frame element R and at least one separating element T
- at least a part of the separating element T is formed integrally with at least a part of the frame element R. This means in particular that at least a part of the separating element T then merges into the frame element R.
- the at least one separating element T and the frame element R are then present in one piece.
- the embodiment of a frame element R has the advantage that it can function as part of the outer wall when assembling the electrolysis cell E.
- This part of the partition wall W does not contact the solutions in the respective interior IKK, IKA or IKM, which is why it would be a waste to use at least one solid electrolyte ceramic FA ZU for this part.
- the part of the partition wall W which is clamped between the outer wall or forms part of it is subject to pressures, which makes the brittle solid electrolyte ceramic FA unsuitable. Instead, a shatter-proof and cheaper material is selected for the frame R.
- the partition wall W can be manufactured by methods known to those skilled in the art.
- an AFK FA can be used as the partition wall W, which is cut or formed according to methods known to those skilled in the art.
- the partition wall W comprises a frame element R or at least one separating element T
- the AFKs enclosed by the partition wall can be placed in a mold, possibly with seals, and the separating element can be poured over liquid plastic and then allowed to solidify (injection molding process). When it solidifies, this then encloses the AFKs.
- the separating element T is cast separately (or in parts) and then seamlessly attached (e.g. glued) to at least two AFKs. 1 .1 .4.5 Arrangement of the partition W in the electrolysis cell E
- the partition wall W is arranged in the electrolysis cell E in such a way that the alkali cation-conducting solid electrolyte ceramic FA enclosed by the partition wall W directly contacts the interior space IKK on the side SKK via the surface OKK.
- the partition wall W comprises at least two AFKs FA, FB, at least one separating element T and optionally a frame element R
- the partition wall W is arranged in the electrolysis cell E such that the alkali cation-conducting solid electrolyte ceramics FA and FB enclosed by the partition wall W and preferably also the separating element T, directly contact the interior space IKK on the side SKK via the surface OKK.
- the partition wall W in the electrolysis cell E is arranged such that when the interior space IKK on the SKK side is completely filled with solution L 2 , the solution L 2 then contacts at least the alkali cation-conducting solid electrolyte ceramic FA enclosed by the partition wall W via the surface OKK, so that ions (e.g. alkali metal ions such as sodium, lithium, potassium) from FA can enter the solution L 2 .
- ions e.g. alkali metal ions such as sodium, lithium, potassium
- the partition wall W comprises at least two AFKs FA, FB, at least one separating element T and optionally a frame element R
- ions e.g. alkali metal ions such as sodium, lithium, potassium
- the partition wall W is arranged in the electrolysis cell E in such a way that the alkali cation-conducting solid electrolyte ceramic FA enclosed by the partition wall W directly contacts the interior space IKA on the side SA/K via the surface OA/MK.
- the partition wall W comprises at least two AFKs FA, FB, at least one separating element T and optionally a frame element R, and if the electrolysis cell E does not comprise a central chamber, this means that the partition wall W is arranged in the electrolysis cell E such that the alkali cation-conducting solid electrolyte ceramics enclosed by the partition wall W, and preferably also the separating element T, directly contact the interior space IKA on the side SA/MK via the surface OA/MK.
- the partition wall W in the electrolysis cell E is arranged such that when the interior space IKA on the side SA/MK is completely filled with solution l_3, the solution L3 then contacts at least the alkali cation-conducting solid electrolyte ceramic FA enclosed by the partition wall W via the surface OA/MK, so that ions (eg alkali metal ions such as sodium, lithium, potassium) from the solution L4 can enter the AFK FA.
- ions eg alkali metal ions such as sodium, lithium, potassium
- the partition wall W comprises at least two AFKs FA, FB, at least one separating element T and optionally a frame element R
- this means that the partition wall W is arranged in the electrolysis cell E such that when the interior space IKA on the side SA/MK is completely filled with solution L 3 , the solution L 3 then contacts at least the two alkali cation-conducting solid electrolyte ceramics FA and FB enclosed by the partition wall W and preferably also the separating element T via the surface OA/K such that ions (e.g. alkali metal ions such as sodium, lithium) from the solution L3 can enter the AFK FA and FB.
- ions e.g. alkali metal ions such as sodium, lithium
- the partition wall W is arranged in the electrolysis cell E in such a way that the alkali cation-conducting solid electrolyte ceramic F ⁇ enclosed by the partition wall W directly contacts the interior space IKM on the side SA/MK via the surface OA/MK.
- the partition wall W comprises at least two AFKs FA, FB, at least one separating element T and optionally a frame element R
- the electrolysis cell E comprises at least one central chamber M
- the partition wall W is arranged in the electrolysis cell E such that the alkali cation-conducting solid electrolyte ceramics enclosed by the partition wall W, and preferably also the separating element T, directly contact the interior space IKM on the side SA/K via the surface OA/MK.
- the partition wall W borders on the interior space IKM of the central chamber KM.
- the partition wall W in the electrolysis cell E is arranged such that when the interior space IKM on the side SA/MK is completely filled with solution L3, the solution L3 then contacts at least the alkali cation-conducting solid electrolyte ceramic FA enclosed by the partition wall W via the surface OA/MK, so that ions (e.g. alkali metal ions such as sodium, lithium, potassium) from the solution L3 can enter the AFK FA.
- ions e.g. alkali metal ions such as sodium, lithium, potassium
- the partition W comprises at least two AFKs FA, FB, at least one separating element T and, if applicable, a frame element R
- ions e.g. alkali metal ions such as sodium, lithium
- Step (a) of the process according to the invention relates to the preparation of a solution Li of an alcoholate MAOR in ROH, where MA is an alkali metal cation and where R is an alkyl radical having 1 to 6 carbon atoms.
- the process is carried out in an electrolysis cell E.
- step (a1) a solution Lz comprising ROH, preferably comprising an alkali metal alcoholate MAOR and ROH, is passed through IKK.
- the solution Lz is preferably free of water.
- “free of water” means that the weight of the water in the solution Lz based on the weight of all alcohols ROH in the solution Lz (mass ratio) is ⁇ 1:10, more preferably e 1:20, even more preferably e 1:100, even more preferably e 0.5:100, even more preferably e 1:1000, even more preferably e 1:10000.
- the mass fraction of MAOR in the solution Lz, based on the total solution Lz is in particular > 0 to 30 wt.%, preferably 0.1 to 20 wt.%, even more preferably 0.2 to 10 wt.%, even more preferably 0.5 to 5 wt.%, most preferably 0.7 to 2 wt.%, most preferably 1 wt.%.
- the mass ratio of MAOR TO ROH is in particular in the range 1 : 1000 to 1 : 5, more preferably in the range 1 : 250 to 3 : 20, even more preferably in the range 1 : 120 to 1 : 8, even more preferably 1 : 100.
- step (a2) a neutral or alkaline aqueous solution L3 of a salt S comprising MA as cation is passed through IKA.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, hydrogen carbonate or carbonate of MA, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- the pH of the aqueous solution L3 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 L3 is preferably in the range > 0 to 20 wt.%, preferably 1 to 20 wt.%, more preferably 5 to 20 wt.%, even more preferably 10 to 20 wt.%, most preferably 20 wt.%, based on the entire solution L3 .
- step (a3) a voltage is then applied between EA and EK.
- 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.
- the area of the solid electrolyte which contacts the anolyte located in the interior IKA of the anode chamber 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 according to the invention is carried out when the interior space IKA of the anode chamber KA is at least partially loaded with L3 and the interior space IKK of the cathode chamber KK is at least partially loaded with L2, so that both L3 and L2 contact the AFKs enclosed by the partition wall W and in particular also contact the separating element T, if the partition wall W comprises such a element.
- step (a3) a charge transport between EA and EK takes place implies that IKK and IKA are simultaneously charged with L 2 and L 3 respectively such that they cover the electrodes E K and E ⁇ to such an extent that the current circuit is closed.
- step (a1) and step (ct2) are carried out continuously and voltage is applied according to step (a3).
- the solution Li is obtained at the outlet AKK, wherein the concentration of MAOR in Li is higher than in L2.
- the concentration of MAOR in Li is preferably 1.01 to 200.2 times, more preferably 5.04 to 100.8 times, even more preferably 10.077 to 50.4 times, even more preferably 18.077 to 20.08 times higher than in L2, most preferably 20.00 times higher than in L2, wherein even more preferably the mass fraction of MAOR in Li and in L2 is in the range 0.1 to 50 wt.%, even more preferably 1 to 20 wt.%.
- the concentration of the cation MA in the aqueous solution L3 is preferably in the range 0.5 to 5 mol/l, more preferably 1 mol/l.
- the concentration of the cation MA in the aqueous solution L4 is preferably 0.5 mol/l lower than that of the aqueous solution L3 used in each case.
- steps (a1) to (a3) of the process according to the invention are carried out at a temperature of 20 °C to 110 °C, preferably 50 °C to 105 °C, more preferably 80 °C to 99 °C, even more preferably 90 °C to 95 °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 IKK, which can be removed from the cell together with the solution Li via the outlet AKK.
- the mixture of hydrogen and solution Li can then be separated in a special embodiment of the present invention using 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 be produced, which can be removed from the cell together with the solution L4 via the outlet AKK.
- oxygen and/or carbon dioxide can also be produced, which can also be removed.
- the mixture of chlorine, oxygen and/or CO2 and solution L4 can then be separated in a special embodiment of the present invention using methods known to those skilled in the art.
- the gases chlorine, oxygen and/or CO2 have been separated from the solution L4, these can then be separated from one another using methods known to those skilled in the art.
- the electrolysis cell E comprises at least one central chamber KM
- the simultaneous steps (ß1), (ß2), (ß3) are carried out.
- the electrolysis cell E comprises at least one central chamber K, and then the simultaneously occurring steps (ß1), (ß2), (ß3) are carried out.
- step (ß1) a solution L2 comprising ROH, preferably comprising an alkali metal alcoholate MAOR and ROH, is passed through IKK.
- the solution L2 is preferably free of water.
- “free of water” means that the weight of the water in the solution L2 based on the weight of all alcohols ROH in the solution L2 (mass ratio) is 1:10, more preferably 1:20, even more preferably ⁇ 1:100, even more preferably 0.5:100.
- the mass fraction of MAOR in the solution L2, based on the total solution L2, is in particular > 0 to 30 wt.%, preferably 0.1 to 20 wt.%, even more preferably 0.2 to 10 wt.%, even more preferably 0.5 to 5 wt.%, most preferably 0.7 to 2 wt.%, most preferably 1 wt.%.
- the mass ratio of MAOR TO ROH in the solution L2 is in particular in the range 1:1000 to 1:5, more preferably in the range 1:250 to 3:20, even more preferably in the range 1:120 to 1:8, even more preferably 1:100. 1 .2.2.2 Step
- step (ß2) a neutral or alkaline aqueous solution L3 of a salt S comprising MA as cation is passed through IKM, then over VAM, then through IKA.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, hydrogen carbonate or carbonate of MA, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- the pH of the aqueous solution L3 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 salt S in the solution L3 is preferably in the range > 0 to
- step (ß3) a voltage is then applied between EA and EK.
- 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 in a standard manner.
- the area of the solid electrolyte which contacts the anolyte located in the middle chamber KM 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 (ß3) of the method according to the invention is carried out when the interior spaces IKA and IKM of both chambers M and KA are at least partially loaded with L3 and the interior space IKK is at least partially loaded with L2, so that both L3 and L2 contact the solid electrolytes enclosed by the partition wall and in particular also contact the separating element T, if the partition wall W comprises such a element.
- step (ß3) a charge transport between E ⁇ and E K takes place implies that IKK, IKM and IKA are simultaneously charged with L 2 and L 3 respectively such that they cover the electrodes E K and E ⁇ respectively to such an extent that the current circuit is closed.
- step (ß1) and step (ß2) are carried out continuously and voltage is applied according to step (ß3).
- the Li solution is obtained at the outlet AKK, wherein the concentration of AOR in Li is higher than in L2.
- the concentration of AOR in Li is preferably 1.01 to 200.2 times, more preferably 5.04 to 100.80 times, even more preferably 10.077 to 50.40 times, even more preferably 18.077 to 20.08 times higher than in L2, most preferably 20.00 times higher than in L2, wherein even more preferably the mass fraction of MAOR in Li and in L2 is in the range 0.1 to 50 wt.%, even more preferably 1 to 20 wt.%.
- the concentration of the cation MA in the aqueous solution L3 is preferably in the range 0.5 to 5 mol/l, more preferably 1 mol/l.
- the concentration of the cation MA in the aqueous solution L4 is preferably 0.5 mol/l lower than that of the aqueous solution L3 used in each case.
- steps (ß1) to (ß3) of the process according to the invention are carried out at a temperature of 20 °C to 110 °C, preferably 50 °C to 105 °C, more preferably 80 °C to 99 °C, even more preferably 90 °C to 95 °C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
- hydrogen is typically produced in the cathode chamber IKK, which can be removed from the cell together with the solution L4 via the outlet AKK.
- the mixture of hydrogen and solution L4 can then be separated in a special embodiment of the present invention using 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 be produced, which can be removed from the cell together with the solution L4 via the outlet AKK.
- oxygen and/or carbon dioxide can also be produced, which can also be removed.
- the mixture of chlorine, oxygen and/or CO2 and solution L4 can then be separated in a special embodiment of the present invention using methods known to those skilled in the art.
- the gases chlorine, oxygen and/or CO2 after the gases chlorine, oxygen and/or CO2 have been separated from the solution L4, they can then be separated from one another using methods known to those skilled in the art.
- steps (ß1) to (ß3) of the process according to the invention brings further surprising advantages.
- steps (ß1) to (ß3) of the process according to the invention the acid-labile solid electrolyte is protected from corrosion without having to sacrifice alcoholate solution from the cathode compartment as a buffer solution, as in the prior art.
- the process according to the invention is therefore more efficient than the procedure described in WO 2008/076327 A1, in which the product solution is used for the middle chamber, which reduces the overall conversion.
- ROH in an optional step (a*) ROH can be at least partially removed from Li ⁇ 21>, whereby either a solution Li* comprising MAO and ROH, wherein Li* has a reduced mass fraction of ROH compared to Li ⁇ 21>, is obtained or MAOR is obtained as a solid F*.
- the at least partial removal of ROH from Li ⁇ 21> in the optional step (a*) can be carried out according to methods known to those skilled in the art, e.g. by means of distillation apparatuses known to those skilled in the art.
- ROH is essentially completely removed from Li ⁇ 21>, this can be done, for example, in distillation apparatus known to those skilled in the art. MAOR is then obtained as a solid F*.
- step (b) of the process (b) according to the invention PET is reacted in a mixture comprising glycol and at least a portion of the MAOR comprised by Li ⁇ 21> or, if step (a*) is carried out, at least a portion of the MAOR comprised by F* or at least a portion of the MAOR comprised by Li* to form bis-(2-hydroxyethyl) terephthalate BHET.
- step (b) the conversion of PET in a mixture comprising glycol and at least a portion of the MAOR comprised of Li ⁇ 21> TO BHET takes place.
- step (b) in which step (a*) is carried out, in step (b) the conversion of PET in a mixture comprising glycol and at least a portion of the MAOR comprised by F* TO BHET takes place, or in step (b) the conversion of PET in a mixture comprising glycol and at least a portion of the MAOR comprised by Li* to BHET takes place.
- PET that needs to be depolymerized
- any PET that needs to be depolymerized can be used as the PET used in step (b) of the process according to the invention.
- PET arises as waste, especially in households, in industry, in the health sector (e.g. hospitals, doctor's offices) or in agriculture.
- the PET to be depolymerized is present in a mixture with other plastics, in particular at least one plastic selected from polyethylene (“PE”), polyvinyl chloride (“PVC”). This is typically the case when PET is to be depolymerized from plastic waste in the method according to the invention.
- the PET is at least partially separated from the other plastics, preferably by sorting, before it is subjected to step (b) of the method according to the invention.
- the PET is subjected to at least one pretreatment step.
- the PET is subjected to at least one pretreatment step selected from chemical pretreatment step, comminution step before it is used in step (b).
- the PET is preferably subjected to at least one pretreatment step selected from at least partial separation from other plastics, preferably by sorting, chemical pretreatment step, comminution step, before it is used in step (b).
- the PET is mixed with other plastics
- the chemical pretreatment step is in particular a washing step.
- a washing step has the advantage that any impurities, in particular food residues, residues of cosmetics and/or body secretions (e.g. blood, sperm, faeces), are removed before step (b) is carried out.
- impurities could reduce the efficiency of the reaction in step (b) and/or impair the purity of the BHET obtained thereby.
- the waste is heated in particular in a washing solution at a temperature in the range of 30 °C to 99 °C, preferably in the range of 50 °C to 90 °C, even more preferably in the range of 70 °C to 85 °C.
- washing solutions are familiar to the person skilled in the art and are preferably selected from: aqueous solution of a surfactant, preferably a non-ionic surfactant; aqueous solution of an alkali metal hydroxide or alkaline earth metal hydroxide, preferably aqueous NaOH.
- the treatment time of the chemical pretreatment step, in particular the washing step is in particular in the range of 1 min to 12 h, preferably in the range of 10 min to 6 h, more preferably in the range of 30 min to 2 h, even more preferably in the range of 45 to 90 min, most preferably 60 min.
- the aqueous solution is separated, e.g. by filtration, and the cleaned PET is preferably washed at least once with water to remove residues of the washing solution.
- the PET waste thus obtained is then dried, in particular in a drying cabinet.
- the temperature used for drying is in particular in the range from 30 to 120 °C, preferably in the range from 50 °C to 100 °C, more preferably in the range from 60 °C to 90 °C, most preferably 80 °C.
- the comminution step has the advantage that the surface area of the PET available for the reaction in step (b) is increased. This increases the reaction rate of the conversion in step (b).
- the comminution can be carried out in equipment known to those skilled in the art, for example a shredder or a cutting mill.
- the PET is decolorized or deliberately colored before it is subjected to step (b). This can be carried out using methods known to those skilled in the art, e.g. decolorization with hydrogen peroxide or coloring with a dye.
- step (b) of the process according to the invention PET is reacted in a mixture comprising glycol and at least a portion of the MAOR comprised of Li ⁇ 21> or, if step (a*) is carried out, at least a portion of the MAOR comprised of F* or at least a portion of the MAOR comprised of Li* TO BHET.
- PET is converted to BHET in a mixture comprising glycol and at least a portion of the MAOR comprised of Li ⁇ 21> or, if step (a*) is carried out, at least a portion of the MAOR comprised of F* or at least a portion of the MAOR comprised of Li*" means that step (b) is carried out in a mixture comprising PET, glycol and at least a portion of the MAOR obtained in step (a) or step (a*) if this step (a*) is carried out.
- the mechanism of PET cleavage to BHET initially involves the nucleophilic attack of the alkoxide anion RO" on the ester bond and cleavage of the polymer PET, which forms the intermediate ester of the terephthalic acid unit with the alcohol ROH, followed by the transesterification of this ester with glycol.
- This is shown schematically below using an ester bond of PET:
- step (a) in the form of the solution Li or, if step (a*) is carried out, the MAOR obtained in step (a*) in the form of the solution Li* or in the form of the solid F*” is abbreviated according to the invention as “the MAOR obtained in step (a) or step (a*)”.
- Step (b) of the process according to the invention can be carried out in any manner familiar to the person skilled in the art.
- the components PET, glycol, the MAOR obtained in step (a) or step (a*) are mixed in any order and the reaction conditions are adjusted, whereby PET is cleaved to BHET according to step (b).
- step (b) PET is mixed with glycol and at least part of the MAOR obtained in step (a) or step (a*) to form a mixture Mi comprising PET, glycol and MAOR, and PET in the mixture Mi is at least partially reacted with glycol and MAOR to form bis(2-hydroxyethyl) terephthalate BHET.
- a mixture M2 is obtained which contains BHET and which in particular additionally comprises glycol, MAOR and optionally unreacted PET and optionally MHET and optionally TS.
- step (b) one or two of the three components selected from PET, glycol, the MAOR obtained in step (a) or step (a*) are initially introduced, the reaction conditions are set therein, and finally the remaining component(s) are added.
- the mixture Mi is obtained in which, since the reaction conditions have already been set, PET is then immediately cleaved to BHET according to step (b), and at the end of step (b) the mixture M2 is obtained, which contains BHET and which in particular additionally comprises glycol, MAOR and optionally unreacted PET as well as optionally MHET and optionally TS.
- step (b) which is carried out in particular in a continuous process, at least one, preferably two, preferably all three of the components selected from PET, glycol, the MAOR obtained in step (a) or step (a*) are fed to a mixture Mi which comprises PET, glycol, the MAOR obtained in step (a) or step (a*) and BHET, i.e. in this mixture Mi the conversion of PET according to step (b) to BHET takes place during the addition of at least one of the three components PET, glycol, the MAOR obtained in step (a) or step (a*).
- a mixture M 2 is obtained which contains BHET and which in particular additionally comprises glycol, MAOR and optionally unreacted PET as well as optionally MHET and optionally TS.
- the reaction in step (b) is carried out in particular at a temperature of at least 100 °C, preferably at a temperature in the range from 100 °C to 197 °C, more preferably at a temperature in the range from 130 °C to 197 °C, more preferably at a temperature in the range from 150 °C to 197 °C, more preferably at a temperature in the range from 175 °C to 197 °C.
- the reaction in step (b) is preferably carried out at the boiling point of the glycol. Even more preferably, glycol is refluxed, i.e. glycol is evaporated from the reaction, condensed and then returned to the reaction. This refluxing can be set using means familiar to the person skilled in the art, for example in a distillation apparatus.
- This embodiment is particularly advantageous when MAOR is added to the mixture in step (b) as a solution in ROH, i.e. in particular in the form of Li or Li*, since the excess alcohol ROH, which has a lower boiling point than glycol, then evaporates from the mixture. This further reduces the occurrence of by-products.
- HTS is the molar amount of TS formed from the beginning of step (b) to time tb in step (b).
- niviHET is the molar amount of MHET formed from the beginning of step (b) to time t& in step (b).
- nBHET is the molar amount of BHET formed from the beginning of step (b) to time tb in step (b).
- MHET also includes the corresponding carboxylate of the structure shown.
- TS also includes the corresponding mono- and dicarboxylate of the structure shown.
- the total weight of the MAOR used in step (b) of the process according to the invention is in particular in the range from 0.1 to 100 wt.%, preferably in the range from 0.5 to 80 wt.%, more preferably in the range from 1.0 to 50 wt.%, more preferably in the range from 1.5 to 25 wt.%, more preferably in the range from 2.0 to 10 wt.%, more preferably in the range from 2.5 to 6.0 wt.%, particularly preferably 3.5 to 5.0 wt.%, most preferably 3.9 wt.%.
- the ratio of the weight [in kg] of the glycol used in step (b) of the process according to the invention, based on the weight [in kg] of the PET used in step (b) of the process according to the invention, is in particular in the range from 1 : 1 to 100 : 1, preferably in the range from 2 : 1 to 50 : 1, more preferably in the range from 3 : 1 to 40 : 1, more preferably in the range from 4:1 to 30:1, more preferably in the range of 5:1 to 20:1, more preferably in the range of 6:1 to 10:1, particularly preferably 7:1 to 9:1, most preferably 8:1.
- step (b) can be carried out using equipment familiar to the specialist.
- the molar ratio q of the amount of BHET (HBHET) to the sum of the amounts of MHET and TS (HMHET + HTS) in the mixture obtained after step (b) is preferably in the range 1:1 to 1000:1, preferably 2:1 to 500:1, more preferably 4:1 to 300:1, even more preferably 10:1 to 100:1, even more preferably 11:1 to 60:1, even more preferably 13:1 to 24:1.
- q nBHEi/ (nwiHET + nis)
- step (c) BHET is at least partially separated from the mixture obtained after completion of step (b), in particular from the mixture M2. This is even more preferably carried out by crystallization and/or distillation. Even more preferably, BHET is filtered off in step (c) from the mixture obtained after completion of step (b) and then crystallized out.
- the BHET obtained in the mixture Mi in the process according to the invention is preferably polymerized to PET in a process for recycling polyethylene terephthalate in one step (Q).
- BHET is polymerized back to PET in step (Q) in the presence of catalysts, which are in particular catalysts selected from the group consisting of antimony compounds, preferably Sb20s.
- the polymerization of BHET to PET in step (Q) is carried out at least at the boiling temperature of the glycol.
- glycol is removed from the reaction mixture during the polymerization in step ( in order to shift the reaction equilibrium to the side of the polymer PET.
- the polymerization of BHET to PET in step (Q) is carried out at the boiling temperature of the glycol. Even more preferably, glycol is then removed from the reaction mixture during the polymerization in step (Q) in order to shift the reaction equilibrium to the side of the polymer PET.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
L'invention concerne un procédé de dépolymérisation de polyéthylène téréphtalate (= "PET"), dans lequel le PET est mis à réagir dans un mélange avec du glycol et de l'alcoolate de métal alcalin produit de manière électrolytique, en particulier de l'alcoolate de lithium, de sodium ou de potassium, pour former du bis-(2-hydroxyéthyl)-téréphtalate (= "BHET"). Le procédé selon l'invention est caractérisé en ce que la proportion de BHET parmi les produits de clivage est particulièrement élevée par rapport à la proportion de produits de clivage indésirables mono-(2-hydroxyéthyl)-téréphtalate (= "MHET") et téréphtalate (= "TS"). Par conséquent, le procédé selon l'invention permet un rendement élevé de BHET, qui peut être utilisé directement pour une nouvelle production de PET. L'invention concerne également un procédé de recyclage de PET, dans lequel le BHET obtenu dans le procédé de dépolymérisation de PET est à nouveau polymérisé pour former du PET, éventuellement après un autre nettoyage.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2022/079048 WO2024083323A1 (fr) | 2022-10-19 | 2022-10-19 | Procédé amélioré de dépolymérisation de polyéthylène téréphtalate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2022/079048 WO2024083323A1 (fr) | 2022-10-19 | 2022-10-19 | Procédé amélioré de dépolymérisation de polyéthylène téréphtalate |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024083323A1 true WO2024083323A1 (fr) | 2024-04-25 |
Family
ID=84360287
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2022/079048 WO2024083323A1 (fr) | 2022-10-19 | 2022-10-19 | Procédé amélioré de dépolymérisation de polyéthylène téréphtalate |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2024083323A1 (fr) |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3222299A (en) | 1961-10-16 | 1965-12-07 | Du Pont | Process of reclaiming linear terephthalate polyester |
US4355175A (en) | 1981-04-06 | 1982-10-19 | Pusztaszeri Stephen F | Method for recovery of terephthalic acid from polyester scrap |
DD258143A3 (de) | 1986-03-03 | 1988-07-13 | Koethen Ing Hochschule | Elektrolysezelle fuer stofftransportgehemmte oder durch konzentrationsabnahmen kinetisch verlangsamte elektrodenreaktionen |
US4831146A (en) | 1988-03-21 | 1989-05-16 | Air Products And Chemicals, Inc. | Process for preparing triacetone amine and other oxopiperidines |
EP0723951A1 (fr) | 1995-01-24 | 1996-07-31 | ARS ING S.r.L. | Procédé de préparation du téréphtalate de bis (2-hydroxyéthyle) |
JP2000309663A (ja) | 1999-04-27 | 2000-11-07 | Asahi Chem Ind Co Ltd | 熱可塑性ポリエステルの分解処理装置及び分解処理方法 |
DE10032899C2 (de) | 2000-07-06 | 2003-09-18 | B & B Anlagenbau Gmbh | Verfahren zum Aufbereiten von PET-Behältnissen mittels einer Wärmebehandlung |
DE10360758A1 (de) | 2003-12-23 | 2005-07-28 | Degussa Ag | Elektrochemische Herstellung von Alkalialkoholaten mit Hilfe einer keramischen Festelektrolytmembran |
US20060226022A1 (en) | 2003-12-11 | 2006-10-12 | Ceramatec, Inc. | Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes |
WO2007048712A2 (fr) | 2005-10-24 | 2007-05-03 | Basf Se | Membranes structurees en surface, membranes revetues de catalyseur et unites membrane-electrode composees de ces membranes |
WO2008076327A1 (fr) | 2006-12-14 | 2008-06-26 | Ceramatec, Inc. | Procédé électrolytique de production d'alcoolates alcalins dans lequel sont utilisés et un séparateur et un électrolyte alcalins conducteurs d'ions |
US20100044242A1 (en) | 2008-08-25 | 2010-02-25 | Sai Bhavaraju | Methods For Producing Sodium Hypochlorite With a Three-Compartment Apparatus Containing an Acidic Anolyte |
DE102010062804A1 (de) | 2010-01-12 | 2011-07-14 | Evonik Degussa GmbH, 45128 | Verfahren zur Herstellung von 1,1 Diarylalkanen und Derivativen davon |
WO2012048032A2 (fr) | 2010-10-07 | 2012-04-12 | Ceramatec, Inc. | Systèmes et procédés chimiques pour faire fonctionner une cellule électrochimique avec un anolyte acide |
WO2014008410A1 (fr) | 2012-07-03 | 2014-01-09 | Ceramatec, Inc. | Appareil et procédé de production de métal dans une cellule électrolytique de nasicon |
US20160204459A1 (en) | 2015-01-13 | 2016-07-14 | Korea Institute Of Science And Technology | Porous nafion membrane and method for preparing the same |
DE102015013155A1 (de) | 2015-10-09 | 2017-04-13 | Forschungszentrum Jülich GmbH | Elektrolytmaterial mit NASICON-Struktur für Feststoff-Natriumionenbatterien sowie Verfahren zu deren Herstellung |
WO2020002999A2 (fr) | 2018-06-25 | 2020-01-02 | 9449710 Canada Inc. | Formation d'esters d'acide téréphtalique |
EP3885470A1 (fr) | 2020-03-24 | 2021-09-29 | Evonik Functional Solutions GmbH | Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres |
US20210301407A1 (en) * | 2020-03-24 | 2021-09-30 | Evonik Functional Solutions Gmbh | Process for preparing sodium alkoxides |
-
2022
- 2022-10-19 WO PCT/EP2022/079048 patent/WO2024083323A1/fr unknown
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3222299A (en) | 1961-10-16 | 1965-12-07 | Du Pont | Process of reclaiming linear terephthalate polyester |
US4355175A (en) | 1981-04-06 | 1982-10-19 | Pusztaszeri Stephen F | Method for recovery of terephthalic acid from polyester scrap |
DD258143A3 (de) | 1986-03-03 | 1988-07-13 | Koethen Ing Hochschule | Elektrolysezelle fuer stofftransportgehemmte oder durch konzentrationsabnahmen kinetisch verlangsamte elektrodenreaktionen |
US4831146A (en) | 1988-03-21 | 1989-05-16 | Air Products And Chemicals, Inc. | Process for preparing triacetone amine and other oxopiperidines |
EP0723951A1 (fr) | 1995-01-24 | 1996-07-31 | ARS ING S.r.L. | Procédé de préparation du téréphtalate de bis (2-hydroxyéthyle) |
JP2000309663A (ja) | 1999-04-27 | 2000-11-07 | Asahi Chem Ind Co Ltd | 熱可塑性ポリエステルの分解処理装置及び分解処理方法 |
DE10032899C2 (de) | 2000-07-06 | 2003-09-18 | B & B Anlagenbau Gmbh | Verfahren zum Aufbereiten von PET-Behältnissen mittels einer Wärmebehandlung |
US20060226022A1 (en) | 2003-12-11 | 2006-10-12 | Ceramatec, Inc. | Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes |
DE10360758A1 (de) | 2003-12-23 | 2005-07-28 | Degussa Ag | Elektrochemische Herstellung von Alkalialkoholaten mit Hilfe einer keramischen Festelektrolytmembran |
WO2007048712A2 (fr) | 2005-10-24 | 2007-05-03 | Basf Se | Membranes structurees en surface, membranes revetues de catalyseur et unites membrane-electrode composees de ces membranes |
WO2008076327A1 (fr) | 2006-12-14 | 2008-06-26 | Ceramatec, Inc. | Procédé électrolytique de production d'alcoolates alcalins dans lequel sont utilisés et un séparateur et un électrolyte alcalins conducteurs d'ions |
US20100044242A1 (en) | 2008-08-25 | 2010-02-25 | Sai Bhavaraju | Methods For Producing Sodium Hypochlorite With a Three-Compartment Apparatus Containing an Acidic Anolyte |
DE102010062804A1 (de) | 2010-01-12 | 2011-07-14 | Evonik Degussa GmbH, 45128 | Verfahren zur Herstellung von 1,1 Diarylalkanen und Derivativen davon |
WO2012048032A2 (fr) | 2010-10-07 | 2012-04-12 | Ceramatec, Inc. | Systèmes et procédés chimiques pour faire fonctionner une cellule électrochimique avec un anolyte acide |
WO2014008410A1 (fr) | 2012-07-03 | 2014-01-09 | Ceramatec, Inc. | Appareil et procédé de production de métal dans une cellule électrolytique de nasicon |
US20160204459A1 (en) | 2015-01-13 | 2016-07-14 | Korea Institute Of Science And Technology | Porous nafion membrane and method for preparing the same |
DE102015013155A1 (de) | 2015-10-09 | 2017-04-13 | Forschungszentrum Jülich GmbH | Elektrolytmaterial mit NASICON-Struktur für Feststoff-Natriumionenbatterien sowie Verfahren zu deren Herstellung |
WO2020002999A2 (fr) | 2018-06-25 | 2020-01-02 | 9449710 Canada Inc. | Formation d'esters d'acide téréphtalique |
EP3885470A1 (fr) | 2020-03-24 | 2021-09-29 | Evonik Functional Solutions GmbH | Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres |
US20210301407A1 (en) * | 2020-03-24 | 2021-09-30 | Evonik Functional Solutions Gmbh | Process for preparing sodium alkoxides |
Non-Patent Citations (7)
Title |
---|
JAVED S ET AL: "Sodium Methoxide as a Low-cost Glycolysis Catalyst for Chemical Recycling of Post-consumer PET Waste", DGMK PETROCHEMISTRY CONFERENCE, 5 October 2022 (2022-10-05), XP093092436 * |
M.A. HICKNERA.M. HERRINGE.B. COUGHLIN: "Part B: Polymer Physics", JOURNAL OF POLYMER SCIENCE, vol. 51, 2013, pages 1727 - 1735 |
N.D. PINGALES.R. SHUKLA, EUROPEAN POLYMER JOURNAL, vol. 44, 2008, pages 4151 - 4156 |
S.A. MAREEVD.YU. BUTYLSKIIN.D. PISMENSKAYAC. LARCHETL. DAMMAKV.V. NIKONENKO, JOURNAL OF MEMBRANE SCIENCE, vol. 563, 2018, pages 768 - 776 |
T. YOSHIOKAN. OKAYAMAA. OKUWAKI, IND. ENG. CHEM. RES., vol. 37, 1998, pages 336 - 340 |
VON N. ANANTHARAMULUK. KOTESWARA RAOG. RAMBABUB. VIJAYA KUMARVELCHURI RADHAM. VITHAL, J MATER SCI, vol. 46, 2011, pages 2821 - 2837 |
VON S.R. SHUKLAA.M. HARAD, JOURNAL OF APPLIED POLYMER SCIENCE, vol. 97, 2005, pages 513 - 517 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2451845C3 (de) | Verfahren zur elektrolytischen Herstellung von Chloraten | |
EP3885470B1 (fr) | Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres | |
EP1894914B1 (fr) | Procédé de fabrication de diarylcarbonates | |
WO2017125469A1 (fr) | Système d'électrolyse et procédé de production d'oxyde d'éthylème par voie électrochimique | |
DE3631561A1 (de) | Loesungen von fluorpolymeren und deren verwendung | |
DE102007058701A1 (de) | Verfahren zur Herstellung von Diarylcarbonat | |
EP3885471A1 (fr) | Procédé amélioré de fabrication d'alcools de sodium | |
WO2024083323A1 (fr) | Procédé amélioré de dépolymérisation de polyéthylène téréphtalate | |
DE2451846A1 (de) | Verfahren zur elektrolytischen herstellung von metallhydroxidloesungen | |
WO2023193940A1 (fr) | Procédé amélioré de dépolymérisation de polyéthylène téréphtalate | |
DE2659581A1 (de) | Fluorierte kationenaustauschermembran und deren verwendung | |
EP4043616B1 (fr) | Procédé de production d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres | |
EP4124675B1 (fr) | Paroi de séparation résistante à la rupture comprenant des céramiques à électrolyte solide pour cellules d'électrolyse | |
DE2434921C3 (de) | Elektrolysezelle und Verfahren zur Elektrolyse ionisierbarer chemischer Verbindungen | |
EP4112778B1 (fr) | Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux | |
EP3449041B1 (fr) | Procédé de conversion électrochimique de composés organiques contenus dans des résidus ou résultants en tant que résidus | |
WO2023006493A1 (fr) | Paroi de séparation résistante à la rupture entourant des céramiques à électrolyte solide pour cellules d'électrolyse | |
EP4112780B1 (fr) | Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux | |
EP4112779B1 (fr) | Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux | |
EP4399348A1 (fr) | Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse | |
WO2023016897A1 (fr) | Procédé de production d'alcoolates de métal alcalin dans une cellule d'électrolyse | |
DE2546194A1 (de) | Membran-elektrolysezelle, insbesondere fuer die chloralkalielektrolyse | |
WO2023030915A1 (fr) | Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse | |
DE2260658C2 (fr) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22808662 Country of ref document: EP Kind code of ref document: A1 |