EP3853396A1 - Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2 - Google Patents
Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2Info
- Publication number
- EP3853396A1 EP3853396A1 EP19765469.2A EP19765469A EP3853396A1 EP 3853396 A1 EP3853396 A1 EP 3853396A1 EP 19765469 A EP19765469 A EP 19765469A EP 3853396 A1 EP3853396 A1 EP 3853396A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- anolyte
- catholyte
- cathode
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 264
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 132
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims description 344
- 239000003792 electrolyte Substances 0.000 claims description 91
- 238000000926 separation method Methods 0.000 claims description 68
- 238000009792 diffusion process Methods 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 25
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000003014 ion exchange membrane Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 13
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 13
- 239000011736 potassium bicarbonate Substances 0.000 claims description 13
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000012824 chemical production Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 110
- 238000009826 distribution Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- -1 hydroxide ions Chemical class 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005341 cation exchange Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 241001479434 Agfa Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JZQLRTAGAUZWRH-UHFFFAOYSA-N 2-aminoethanol;hydrate Chemical compound [OH-].[NH3+]CCO JZQLRTAGAUZWRH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Inorganic materials [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 description 1
- 238000004056 waste incineration Methods 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/083—Separating products
-
- 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
- C25B15/087—Recycling of electrolyte to electrochemical cell
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- 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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
-
- 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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- CO2 is also helpful to use as a raw material for the synthesis. This avoids the release of CO2 from various processes such as steel production or e.g. waste incineration. This could slow the rise in global warming.
- the new process is a particularly sustainable process.
- Electrolysers such as those used in chlor-alkali electrolysis, usually have an electrode area of more than 1 m 2 per electrolysis cell. Over 100 electrolysis cells are connected to form an electrolyser. Several electrolysers are then used for production at one location.
- the object of the present invention was therefore to provide a device and a method for operating a gas diffusion electrode on an industrial scale, in which CO2 is converted at the GDE.
- the technical scale is understood to mean production quantities in which more than 0.1 kg CO2 / h * m 2 are converted electrochemically.
- the separator is an ion exchange membrane or a diaphragm, particularly preferably the separator is an ion exchange membrane.
- diaphragms which are known in principle and which separate the anode compartment from the cathode compartment, especially from the cathode gap, are particularly suitable as the diaphragm.
- the diaphragm should in particular have a gas tightness (bubble point) of more than 10 mbar, preferably more than 300 mbar, particularly preferably more than 1000 mbar.
- the diaphragm should continue to be inert to the electrolyte and the reaction gases and stable at the operating temperatures.
- Diaphragms for electrolysis are generally known from the prior art.
- the electrolysis cell is intended for electrolysis on an industrial scale, which means in particular that the overall height of the electrolysis cell is at least 30 cm and thus differs significantly from laboratory and test cells.
- the vertical main dimension of the cathode is at least 30 cm, preferably at least 60 cm, particularly preferably at least 100 cm.
- a gas diffusion electrode is particularly preferably used as the cathode, which contains an electrocatalyst for CO2 reduction, which is produced in particular on the basis of silver and / or silver oxide, preferably on the basis of silver particles as electrocatalyst, and with a powdery fluoropolymer, in particular PTFE powder, as a non-conductive Binder is compactly applied to a metallic or non-metallic, conductive or non-conductive carrier.
- a metallic, conductive carrier is preferably used for compacting.
- polymer powders with comparable properties i.e. in particular inert towards electrolyte at reaction temperature and high current density and which can be processed in the production of the GDE
- polyalkylenes particularly preferably polyethylene, polypropylene or partially fluorinated polymers.
- a means for braking the flow of the catholyte flow hereinafter called the flow brake, is provided in the gap between the membrane and the GDE.
- the flow brake is particularly preferably designed as an electrically non-conductive, inert textile fabric.
- the flow brake can in particular consist of a porous textile fabric, particularly preferably a woven, knitted or knitted fabric, which is arranged in the gap.
- a porous textile fabric particularly preferably a woven, knitted or knitted fabric, which is arranged in the gap.
- mechanical installations in the gap are also conceivable, which are horizontal or for
- the catholyte can preferably be supplied via a distribution channel which connects the catholyte feed line to the gap.
- a distribution channel which connects the catholyte feed line to the gap.
- it can have an overflow (not shown in the figures), via which excess electrolyte, if any, can be removed.
- the gas diffusion electrode seals the distribution channel and the gap from the gas space in a gas-tight manner.
- Sub-stoichiometric amounts of CO2 are required if more hydrogen is to be deliberately produced. If the production of hydrogen is to be avoided, excess CO2 is added.
- the amount of CO2 is preferably a multiple of the stoichiometric amount required after the flowing electrical current. In particular 0.5% to 800% more CO2 is added than is required stoichiometrically.
- the second gas discharge line is connected to a separation device for separating carbon dioxide from oxygen and the separation device is connected to the gas supply line via a carbon dioxide line in order to be able to return separated carbon dioxide to the electrolysis cell. Due to its purity, the separated oxygen can be used directly for further use in other chemical reactions.
- an aqueous solution of alkali hydrogen carbonate preferably potassium hydrogen carbonate, cesium hydrogen carbonate or sodium hydrogen carbonate, particularly preferably potassium hydrogen carbonate, is used as the catholyte.
- an aqueous solution of alkali hydrogen carbonate preferably potassium hydrogen carbonate
- Cesium bicarbonate or sodium bicarbonate particularly preferably potassium bicarbonate used.
- the salts in the anolyte and catholyte expediently have, in particular, the same cations.
- both the anolyte and the catholyte, conductive salts can be added, which are inert to the anode reaction or the cathode reaction, e.g. As alkali sulfates, or alkali hydrogen sulfates, especially optionally potassium, cesium or sodium sulfate or - hydrogen sulfate, particularly preferably potassium hydrogen sulfate.
- the total concentration of the salts is preferably 0.1 to 2 mol per L, electrolytes with a conductivity at 25 ° C. of greater than 10 S / m being used in particular (S stands for Siemens and m for meters).
- the catholyte drain is attached to the lower end of the gap and the catholyte inlet is attached to the cathode half-shell above the gap and the catholyte drain is connected to a catholyte collecting pipe the catholyte from the catholyte outlet of the electrolytic cells is combined.
- the anolyte from the anolyte outlet of the electrolytic cells is brought together in a collecting tube for anolyte (see, for example, FIG. 1).
- both solutions are preferably each fed to a gas separation unit.
- gas dissolved and dispersed in the electrolyte is separated.
- the anolyte is essentially freed from oxygen, the catholyte from carbon monoxide and hydrogen. This prevents the anolyte from being mixed with oxygen containing CO2 and the catholyte containing gas containing CO / H2 and the formation of explosive gas mixtures.
- the electrolytes freed from gases: anolyte and catholyte can then be combined.
- the electrolytes can be heated by means of heat exchangers, if necessary be cooled.
- Appropriate amounts of electrolyte salt or water can be added to adjust the concentration of the electrolyte if necessary. More concentrated or dilute electrolyte solutions can also be added to adjust the desired input concentration into the electrolytic cell
- the first gas discharge line in particular via a collecting line which connects the first gas discharge line of the electrolysis cell to other identical gas discharge lines from other electrolysis cells, is connected to a gas separation unit for separating carbon monoxide, hydrogen and unused carbon dioxide gas.
- the gas separation unit further preferably has a discharge line for separated carbon monoxide, which is connected to a chemical production plant for the chemical conversion of carbon monoxide into chemical intermediate products.
- the separated carbon monoxide can be sent to a manifold or a storage facility for further use.
- the second gas discharge line for the anode reaction product is connected to a second gas separation unit for separating carbon dioxide from oxygen, and the second gas separation unit is connected to the gas supply line via a carbon dioxide line, and possibly via a distributor pipeline.
- the second gas discharge line for the anode reaction product and the anolyte outlet form a unit and are connected to a gas / liquid separation and an outer collecting pipe.
- the gas / liquid separation separates the gas mixture of CO2 and O2 from the electrolyte.
- the anolyte is fed to the second gas separation unit and the gas to the second gas separation unit from CO2 and O2.
- the electrolyte from the electrolyte collecting device is then fed back to the anolyte inlet via the outer anolyte distributor pipeline.
- the electrolyte return line (optionally for catholyte and / or anolyte) has a supply line for the admixture of optionally water or a higher concentration electrolyte and a mixing unit for the mixing of the depleted electrolyte (eg the anolyte) with higher concentrated electrolyte on or as required for the addition of water or low-concentration electrolyte.
- Another object of the invention is an electrolyzer for the electrochemical conversion of CO2 on an industrial scale according to the membrane electrolysis process or diaphragm electrolysis process, characterized in that the electrolyzer has a plurality of electrolysis cells according to the invention which are electrically connected to one another in a bipolar manner.
- connections of the anolyte or catholyte feed lines and the corresponding electrolyte discharge lines of the individual electrolysis cells are preferably connected to one another via distributors or collectors via external connecting pipelines.
- a further preferred embodiment of the new electrolyser is characterized in that, for connecting the supply and discharge lines of the several electrolysis cells to one another, collectors for anolyte, collectors for catholyte, distributors for anolyte, distributors for catholyte and gas distributors for reaction gas and gas collectors for product gases are provided.
- the leads of at least 10 electrolysis cells are connected in a distributor and in particular the leads of at least 4 electrolysis cells are connected in a collector.
- the anolyte supply takes place via a distributor pipe for the anolyte.
- the anolyte is fed to the elements connected to the anode compartment via a particularly flexible connection, for example a hose.
- the anolyte which is led out of the anode compartment and the gas generated therein (main constituent oxygen and carbon dioxide) are again fed to a collecting pipeline.
- This outer collecting pipeline can act as a gas / liquid separator, so that gas can be fed via an additional separate line to an optional second gas separation unit for separating oxygen and carbon dioxide.
- the anolyte is fed from the connecting pipeline to the second gas separation unit and then to the electrolyte collection device.
- the gas is preferably supplied to the cathode compartment (see, for example, FIG. 5) via an outer distributor pipeline. From this outer distribution pipeline, the gas is supplied via a connection to the cathodes connected to it via the gas supply.
- the connection from the cathode half-cell to the distributor pipeline can take place, for example, via a flexible hose.
- the gas can be distributed over the width of the electrolysis cell within the electrolysis cell, so that the gas flows evenly from bottom to top and the GDE can be supplied with a sufficient amount of carbon dioxide gas.
- internals can be made in the gas space, which allow the gas flow to be swirled.
- the gas from the gas space returns to an outer collecting pipe via the outlet.
- the connection between the cathode outlet and the collecting pipeline can again be made via a hose.
- the gas from the outer manifold is fed to a gas separator to separate CO, H2 and unreacted CO2. Separated C0 2 gas from the gas separation device is fed back to the cathode compartment together with fresh carbon dioxide gas via the outer distributor pipeline.
- carbon dioxide is preferably supplied to the gas space in such a way that a
- Gas velocity near the back of the gas diffusion electrode from 0.001 to 15 m / s, preferably from 0.01 to 10 m / s.
- the gas velocity is calculated from the
- the gas quantity setting is at least 0.5 times the stoichiometrically required CO2 quantity calculated according to the flowing electrical current and the resulting quantity of charge.
- the gas velocity is preferably kept constructively in the range defined above from 0.001 to 15 m / s, preferably from 0.01 to 10 m / s. This can e.g. B. take place so that the gas space in the area between the gas diffusion electrode and the support structure for the gas diffusion electrode is kept as narrow as possible.
- the distance between the two gas diffusion electrodes is kept constructively in the range defined above from 0.001 to 15 m / s, preferably from 0.01 to 10 m / s.
- the gas diffusion electrode to the cathode rear wall is therefore at most 5 cm, preferably at most 4 cm, particularly preferably at most 2 cm.
- Flow-carrying internals in the area between the gas diffusion electrode and the support structure for the gas diffusion electrode are also available
- the separation of the anode and cathode chambers by means of the separator serves to avoid the mixing of the electrolytes and to avoid the electrochemical short circuit.
- the anodically formed gas could be reduced again directly at the cathode without a separator, which would result in an electrochemical short circuit, the current efficiency would be reduced and the economy of the process would be impaired.
- the hydrogen and / or carbon monoxide formed at GDE could be explosive with the anodically formed oxygen
- ion exchange membranes can be used
- diaphragms can be used for the electrolysis, for example the diaphragm of the type Zirfon TM Pearl (manufacturer Agfa) made of PFTE and zirconium dioxide is used in particular.
- Zirfon TM Pearl manufactured of PFTE and zirconium dioxide is used in particular.
- the electrolysis cell is expediently constructed in such a way that the separator lies directly on the anode.
- the anode is electrically connected to the anode half-shell.
- the anode is preferably designed in such a way that it has cavities which are shaped in such a way that the gas formed on the anode (for example oxygen gas) conducts to the rear of the anode facing away from the separator.
- the gas formed on the anode for example oxygen gas
- Either an expanded metal, for example, or other anode structures generally known from the prior art can be used as the anode structure.
- a preferred embodiment of the new electrolytic cell is also characterized in that the anode rests on the separator with point, line or sheet-like contact points on the anode.
- the differential pressure with which the separator is pressed onto the anode is at least 10 mbar.
- Another object of the invention is also a process for the electrochemical conversion of CO2 on an industrial scale according to the membrane electrolysis process on a
- Gas diffusion electrode as a cathode characterized in that the method is carried out in the new electrolytic cell described above, the separator being a
- Ion exchange membrane is, with the steps:
- anode reaction product consisting of anolyte and product gas, anolyte being discharged through the anolyte and product gas oxygen and possibly CO2 through the second gas discharge line or, particularly preferably, anolyte and product gas being removed together via a line,
- Another object of the invention is a process for the electrochemical conversion of CO2 on an industrial scale according to the diaphragm electrolysis process on a gas diffusion electrode as a cathode, characterized in that the process is carried out in the new electrolysis cell described above, the separator being a diaphragm, with the steps: - Introducing the catholyte, an aqueous solution containing at least
- anode reaction product consisting of anolyte and product gas, anolyte being discharged through the anolyte outlet and product gas oxygen and possibly CO2 through the second gas discharge line or, particularly preferably, anolyte and product gas being carried off together via a line,
- the carbon dioxide gas is moistened with water vapor before it is fed into the electrolysis cell and into the gas space.
- the carbon dioxide gas is loaded with so much water that the water vapor partial pressure of the catholyte in the cell is equal to that of the water vapor partial pressure
- Gas diffusion electrode from 0.001 m / s to 15 m / s, preferably from 0.01 m / s to 10 m / s.
- Fig. 1 shows a schematic vertical cross section through an electrolytic cell Z
- Fig. 2 shows the anolyte supply and discharge with a common sequence of several electrolytic cells
- Fig. 3 shows the anolyte inlet and outlet with separate processes of several electrolytic cells
- GDE Cathode
- Anode compartment an anolyte
- Electrolyte collecting device second gas separation unit for the separation of C0 2 0 2
- the cathode half-shell 1 has an electrolyte inlet 13 and an electrolyte outlet 14 as well as a gas supply 5 and a gas outlet 6 (see FIG. 1).
- the electrolyte feed 13 to the cathode half-shell 1 takes place from above and the supplied catholyte 17 flows from top to bottom along the gas diffusion electrode (GDE) 11.
- the catholyte 17 flows in the gap 12 between the ion exchange membrane 3 and the GDE 11 downwards.
- a flow brake 24 is mounted in the gap 12.
- the flow brake 24 is made of a porous fabric made of PTFE as in the
- the contacting of the GDE 11 with the power supply line 31 in the cathode space takes place via an elastically mounted, electrically conductive structure 35.
- This elastic structure 35 rests on a rigid nickel-metal structure in the form of an expanded metal (not shown in FIG. 1).
- the expanded metal is electrically conductively connected to the cathode half-shell 1 by a rigid connection 91.
- the GDE 11 is mounted on the elastic structure 35 and is electrically contacted from the side of the gas space 4.
- the cathode half-shell 1 is either in the bipolar connection of a plurality of electrolysis cells ZI, in electrical contact with an anode half-shell 2 of another neighboring electrolysis cell Z2 or with the current supply plate 62. Accordingly, the outermost anode half-shell 2 is electrically connected to the current discharge plate 63.
- the gas discharge lines 7 for the anode gas are collected, which can also take place via a collecting pipeline (not shown) and fed to the second gas separation unit 20 (FIG. 3), or the anode gas is discharged together with the anolyte via common lines 70 from the anode space 15 and in Collector 41b, which is designed as a gas / liquid separation device, is separated into an electrolyte stream (in line 9a) and the anode gas (in line 41a) (FIG. 2). The anode gas is then fed via line 41a to the second gas separation unit 20 for the separation of oxygen and CO2.
- the catholyte brought together in the collector 43 via the catholyte outlet 14 is preferably fed via a catholyte outlet 14a to a gas separation 74, in which the remaining dissolved or dispersed hydrogen and carbon monoxide are freed from the catholyte (see FIG. 6). These gas residues are discarded or burned.
- An oxygen-free electrolyte is removed from the gas separation 72 via the outlet 9b and fed to an electrolysis collecting device 19.
- water or a more dilute or concentrated electrolyte solution 18 can be used to distribute the electrolyte to anodes and cathodes.
- the electrolyte collecting device 19 the electrolyte is brought to the necessary inlet temperature via heat exchangers (not shown) and fed to the electrolysis cells via lines 8 and 13 via distributors 42 and 40 (see FIG. 6).
- the anolyte brought together in the collector 41 via the outlet 9 is preferably fed to a gas separation 72 via the line 9a, in which the anolyte is freed of residual gases such as oxygen. These gas residues are discarded or reused depending on the amount.
- the oxygen-free anolyte is fed via line 9b to an electrolyte collecting device 19.
- Known blow-out columns can in principle serve as the gas separation 72 or 74.
- An electrolysis cell Z with an active electrode area of at least 0.1 m 2 is used as the basis for operation.
- the electrolysis cell Z has a width of at least 10 cm.
- the height of the electrode is at least 30 cm.
- the electrolyte exposure to the GDE is typically 25 L / (h * m 2 ) to 500 L / (h * m 2 ).
- L stands for the delivered volume of catholyte in liters, h for hour and m 2 for the area of the installed GDE.
- the gap 12 between GDE 11 and separator (ion exchange membrane 3) has a gap width of at least 0.1 mm and is at least 30 cm high and 10 cm wide.
- Other salts can be added as conductive salts, such as alkali metal sulfates or hydrogen sulfates.
- the total concentration of the salts is preferably 0.1 to 2 mol per liter, the electrolytes having a conductivity at 25 ° C. of greater than 10 S / m being used (S stands for Siemens and m for meters). The conductivity can be measured using standard conductivity meters.
- the outlet temperature of the catholyte from the cathode half-shell 1 above 14 is in particular a maximum of 85 ° C., preferably a maximum of 60 ° C., particularly preferably a maximum of. 45 ° C.
- the temperature of the catholyte 17 supplied to the cell Z is regulated so that the outlet temperature can be maintained.
- CO2 33 is supplied in excess to the gas space 4 of the cathode half-switch 1 via the inlet 5.
- the amount of CO2 is preferably a multiple of the stoichiometric amount required after the flowing electrical current. 0.5% to 800% more CO2 is added than is stoichiometrically required.
- Gas distribution system in the form of a hose (not shown here) with holes can be used to achieve an even distribution of the supplied CO2 and the
- the catholyte 17 removed from the cathode half-shell 1 via the cathode outlet 14 may possibly still contain residues of the gas mixture formed from CO, H2 and excess CO2.
- a first separation will take place, for example, in a sufficiently dimensioned collecting pipeline 43, in which the gas / liquid mixture is fed from the electrolysis cell Z.
- the collecting pipe 43 has at least one liquid drain 14a and one
- Gas discharge channel (not shown).
- the gas discharge duct stands with one
- Gas manifold 45 in connection.
- the gas manifold 45 is connected to the gas outlet 6 of the cathode element 1.
- the gas manifold 45 leads the gas from all
- Electrolysis cells Z of the gas separation unit 21 are Electrolysis cells Z of the gas separation unit 21.
- the catholyte 17 from the gas collecting line 43 is fed via the line 14a in particular to a gas separation unit 74.
- the electrolyte is returned to the electrolytic cell Z from the electrolyte collecting device 19.
- the composition of the electrolyte can be checked beforehand and, if necessary, supplemented with water and the salts mentioned above, so that the electrolyte is always the same
- the electrolyte is fed back to the electrolytic cell Z, for example by means of a pump via a heat exchanger and the distribution pipes 40, 42.
- the further processing of the separated gas mixture from the outer collecting pipeline 45 consisting of CO, H2 and excess CO2 from the electrolysis cells Z is carried out, for example, as follows:
- the condensate generated during cooling can e.g. be fed back into the electrolyte circuit.
- a cold box is a generally known cold chamber that is operated at low temperatures to separate CO from H2. A temperature of -180 ° C and below is reached in these processes. These cold chambers are used for the separation of synthesis gas and can be designed commercially to be user-specific
- the hydrogen obtained from the cold box is used for further use.
- the carbon monoxide obtained from the cold box will be used for further purposes, for example for the production of phosgene and secondary products for polymer production.
- a silver-based GDE in analogy to the electrode described in EP2398101 with the variation shown below is particularly preferably used as the gas diffusion electrode (GDE) for the CO2 to CO reduction.
- the porosity of the catalytically active layer, calculated from the material densities of the raw materials used, is more than 10%, but less than 80%.
- the GDE is produced as follows:
- the carrier element was a wire mesh made of silver with a wire thickness of 0.14 mm and a mesh width of 0.5 mm.
- the application was carried out with the aid of a 2 mm thick template, the powder being applied using a sieve with a mesh size of 1.0 mm. Excess powder that protruded beyond the thickness of the template was removed using a scraper. After removing the template, the carrier with the applied powder mixture is pressed using a roller press with a pressing force of 0.45 kN / cm pressed.
- the gas diffusion electrode was removed from the roller press.
- the gas diffusion electrode had a porosity of about 50%.
- Electrolytes and avoidance of electrochemical short circuit The anodically formed gas could be reduced again directly at the cathode without separators, thereby creating a
- the hydrogen and / or carbon monoxide formed at GDE could form explosive gas mixtures with the anodically formed oxygen.
- Separators can particularly preferably be used with cation exchange membranes such as fumasep F 1075-PK from Fumatech or the type Nafion N 324 (manufacturer Chemours Company), in particular Nafion N324.
- cation exchange membranes such as fumasep F 1075-PK from Fumatech or the type Nafion N 324 (manufacturer Chemours Company), in particular Nafion N324.
- the structure Zirfon TM Pearl (manufacturer Agfa) made of PFTE and zirconium dioxide is suitable as a diaphragm.
- a cation exchange membrane Nafion N324 is used as an example.
- the electrolysis cell is constructed in particular in such a way that the separator rests on the anode structure.
- the anode is designed so that it has cavities that conduct the gas formed on the anode to the side facing away from the separator.
- an anode structure e.g. an expanded metal can be used, wherein other structures known from the prior art can be used.
- the anolyte 15a is fed in the lower section into the anode compartment 15 via the anolyte inlet 8 and removed in the head part of the anode compartment 15 via the anolyte outlet 9.
- catholyte 17 and anolyte 15a pass through the electrolytic cell Z in countercurrent.
- the anolyte 15a is selected depending on the anode reaction. In the present case, in which oxygen is developed at the anode 10, the same electrolyte is used as anolyte 15a as as catholyte 17.
- the anolyte 15a supplied to the anode half-shell 2 therefore consists, for example, of an electrolyte containing aqueous alkali metal bicarbonate, to which other inert salts are also added to increase the conductivity.
- alkali sulfates include alkali hydrogen sulfates, or mixtures thereof.
- the total concentration of the alkali ions in the electrolyte solution is in particular 0.01 mol / L to 2 mol / L.
- the pH of the anolyte 15a fed to the anode half-switch is preferably 4 to 9
- a volume flow of the anolyte 15a is fed to the anode half-shell via the inlet 8, in particular in the range from 10 L / (h * m 2 ) to 300 L / (h * m 2 ).
- the outlet temperature of the electrolyte from the anode half-shell is preferably at most 85 ° C., preferably max. 60 ° C, particularly preferably a maximum of 45 ° C.
- the temperature of the anolyte supplied to cell Z is regulated via a heat exchanger so that the outlet temperature can be maintained.
- the mixture of oxygen formed and possibly carbon dioxide and the anolyte removed from the anode half-shell 2 is first fed via lines 70 to an outer header pipe 41b.
- the collecting pipeline 41b has at least one liquid outlet 9a and a gas discharge channel 41a.
- Anode half-shell 2 led out, possibly dried and fed to second gas separation unit 20.
- the CO2 separated in the second gas separation unit 20 becomes the gas space 4
- the anolyte 15a is led out of the anode half-shell 2 via line 9 and onto a
- the anolyte 15a is left of residual oxygen and CO2 gas Collective pipeline separated.
- the anolyte is then fed via line 9a to a gas separation unit 72 for the oxygen for residual degassing.
- the anolyte freed of residual oxygen is fed to an electrolyte collecting device 19 via a line 9b.
- the catholyte 17 running out of the cathode half-shell 2 via the outlet 14 is fed to an outer collecting pipe 43 (FIG. 4). Possibly. entrained carbon monoxide or hydrogen are fed from the manifold 43 via a line (not shown) to the manifold 45 for CO / H2.
- the catholyte 17 passes via line 14a to remove residual CO / H2 into a gas separation unit 74.
- the catholyte freed of CO and H2 is fed via line 14b to the electrolyte collecting device 19.
- Electrolysis cell Z supplied.
- the composition of the electrolyte is checked beforehand and, if necessary, supplemented with water and / or the salts mentioned above via the feed line 18, so that anolyte 15a and catholyte 17 always have the same concentration of the electrolysis cell Z
- the electrolyte is removed from the electrolyte collecting device 19 by means of a pump and fed to the anode half-shell via heat exchangers and the connecting pipelines, and to the cathode half-shell via a further heat exchanger (not shown).
- Plastics such as polypropylene, polyethylene or PTFE (polytetrafluoroethylene) can preferably be used.
- the voltage across the electrolysis cells is set on the rectifier so that a current of 7590 A flows.
- a 15% by weight potassium bicarbonate solution 17 with a mass flow of 600 kg / h and a temperature of 30 ° C. is fed to the cathode half-shell 1 via the feed line 13.
- the temperature of the solution running out of the cathode half-shell 1 via the discharge line 14 is 45.3 ° C. and has a potassium hydrogen carbonate content of 18.5% by weight.
- the mass flow is 640.1 kg / h.
- the anolyte 15a running out of the anode half-shell 2 is fed to an outer collecting pipeline 41. From the outer collecting pipe 41, the anolyte 15a is fed to a gas separator 72 for the removal of remaining amounts of oxygen.
- the gas separation unit 72 consists of a blow-out column (not shown) with a diameter of 50 cm and a height of 200cm. In countercurrent, the catholyte nitrogen introduced from above via a distributor nozzle is counter-flowed at a volume flow of 100 L / h. 0 2 -free electrolyte can be removed from the blow-out column and fed to the electrolyte collecting device 19.
- the catholyte 17 running out of the cathode half-shell 1 via the line 14 is fed to an outer collecting pipe 43.
- the catholyte 17 is connected to a gas separation unit 74 via the line 14a.
- the gas separation unit 74 consists of a blow-out column (not shown) with a diameter of 50 cm and a height of 200 cm.
- the catholyte nitrogen introduced from above via a distributor nozzle is counter-flowed at a volume flow of 100 L / h.
- CO and H2-free catholyte 17 are removed from the blow-out column and fed to the electrolyte collecting device 19 via line 14b.
- the blown gases are fed to a combustion unit.
- a mass flow of 36511 g / h of CO2 is supplied to the gas space 4 of the cathode half-shell 1 via the gas feed line 5.
- the amount corresponds to approximately 5.8 times the stoichiometrically required CO2.
- the temperature is 25 ° C.
- the CO2 is saturated with water at 25 ° C. This is done by injecting water into the feed line 5.
- the gas velocity of the CO2 in the gas space is approx. 0.06 m / s at 25 ° C. The proportionate amount of gas from water vapor was not taken into account in the calculation.
- the reaction gas mixture is fed to the gas space 4 via the discharge line 6 of a gas manifold 45.
- the gas from the gas manifold 45 is fed to a gas separation unit 21 for the separation of CO, H2 and excess or unreacted CO2 (Lig. 5).
- the gas mixture has the following composition: carbon monoxide: 2577 g / h, hydrogen 99 g / h, CO2 20000 g / h.
- the separated CO2 33 is fed to a gas return line 53 and is returned to the gas supply 5 to the cathode half-shell 1 via a gas distribution line 44.
- a partial stream of the CO / H2 mixture from the first stage of gas separation in the gas separation unit 21 is fed to the chemical synthesis of methanol (not shown).
- the remaining CO / H2 mixture is fed to the second stage of the gas separation unit 21, which separates hydrogen and CO.
- the separated gases are fed to further chemical syntheses, in particular the CO is fed to a process for the production of isocyanate, in which phosgene is produced from CO with chlorine in a first step and the phosgene obtained is further processed to isocyanates.
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Abstract
Description
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Applications Claiming Priority (2)
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EP18195279.7A EP3626861A1 (de) | 2018-09-18 | 2018-09-18 | Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2 |
PCT/EP2019/073789 WO2020057998A1 (de) | 2018-09-18 | 2019-09-06 | Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2 |
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EP18195279.7A Ceased EP3626861A1 (de) | 2018-09-18 | 2018-09-18 | Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2 |
EP19765469.2A Pending EP3853396A1 (de) | 2018-09-18 | 2019-09-06 | Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2 |
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EP (2) | EP3626861A1 (de) |
JP (1) | JP2022500558A (de) |
KR (1) | KR20210060468A (de) |
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AU2019210132B2 (en) | 2018-01-22 | 2023-02-02 | Twelve Benefit Corporation | System and method for carbon dioxide reactor control |
EP4189142A1 (de) * | 2020-07-28 | 2023-06-07 | Électro Carbone Inc. | Elektrochemische zelle zur kohlendioxidreduktion in richtung flüssiger chemikalien |
EP4189143A2 (de) * | 2020-08-03 | 2023-06-07 | Twelve Benefit Corporation | System und verfahren zur steuerung eines kohlendioxidreaktors |
JP7176026B2 (ja) * | 2021-03-11 | 2022-11-21 | 本田技研工業株式会社 | 電気化学反応装置 |
CN113834224B (zh) * | 2021-09-29 | 2023-10-31 | 西安交通大学 | 基于太阳能的锅炉烟气处理***及方法 |
DE102021128017A1 (de) * | 2021-10-27 | 2023-04-27 | Texotex Ug (Haftungsbeschränkt) | Textiles Flächengebilde |
WO2023154765A2 (en) * | 2022-02-08 | 2023-08-17 | Verdagy, Inc. | Nanoporous membrane support in an electrolyzer cell |
WO2023228254A1 (ja) * | 2022-05-23 | 2023-11-30 | 株式会社 東芝 | 二酸化炭素電解装置 |
JP2023175338A (ja) * | 2022-05-30 | 2023-12-12 | 株式会社東芝 | 一酸化炭素製造装置 |
WO2024035474A1 (en) | 2022-08-12 | 2024-02-15 | Twelve Benefit Corporation | Acetic acid production |
EP4345094A1 (de) | 2022-09-30 | 2024-04-03 | Covestro Deutschland AG | Verfahren zur phosgen-herstellung mit rückführung von kohlendioxid aus wertstoffrecycling |
CN116083933B (zh) * | 2022-12-06 | 2024-03-19 | 南京大学 | 一种二氧化碳电催化反应***及反应方法 |
CN115672020B (zh) * | 2022-12-12 | 2023-02-28 | 中国科学院西北生态环境资源研究院 | 烟道废气中二氧化碳捕集分离催化装置及其控制方法 |
DE102022004678A1 (de) | 2022-12-13 | 2024-06-13 | Covestro Deutschland Ag | Verfahren zur Elektrolyse von Kohlendioxid mit Vorreduktion einer Silberoxid-enthaltenden Gasdiffusionselektrode |
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DE10159372A1 (de) * | 2001-12-04 | 2003-06-12 | Bayer Ag | Gaszuführung bei Elektrolyseprozessen |
ITMI20012379A1 (it) * | 2001-11-12 | 2003-05-12 | Uhdenora Technologies Srl | Cella di elettrolisi con elettrodi a diffusione di gas |
DE102005023615A1 (de) | 2005-05-21 | 2006-11-23 | Bayer Materialscience Ag | Verfahren zur Herstellung von Gasdiffusionselektroden |
DE102005027735A1 (de) | 2005-06-16 | 2006-12-21 | Bayer Materialscience Ag | Elektrochemische Zelle |
DE102010030203A1 (de) | 2010-06-17 | 2011-12-22 | Bayer Materialscience Ag | Gasdiffusionselektrode und Verfahren zu ihrer Herstellung |
JP2012025601A (ja) * | 2010-07-21 | 2012-02-09 | Sharp Corp | 二酸化炭素分離装置およびその使用方法 |
CN103160849B (zh) * | 2011-12-12 | 2016-06-08 | 清华大学 | 二氧化碳电化学还原转化利用的方法 |
US10329676B2 (en) * | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
WO2015139129A1 (en) * | 2014-03-17 | 2015-09-24 | Sean Huff | Gas-contacting electrodes for use in continuous electrochemical reactors and method of making the same |
CA2950294C (en) * | 2014-05-29 | 2022-07-19 | Liquid Light, Inc. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
CN105316700B (zh) * | 2014-07-29 | 2017-11-14 | 中国科学院大连化学物理研究所 | 一种电化学还原二氧化碳反应用电解池及应用 |
DE102015212504A1 (de) * | 2015-07-03 | 2017-01-05 | Siemens Aktiengesellschaft | Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung |
CN205329170U (zh) * | 2015-11-16 | 2016-06-22 | 昆明理工大学 | 一种将二氧化碳电还原为一氧化碳的多室隔膜电解装置 |
DE102016211824A1 (de) * | 2016-06-30 | 2018-01-18 | Siemens Aktiengesellschaft | Anordnung für die Kohlendioxid-Elektrolyse |
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JP2022500558A (ja) | 2022-01-04 |
EP3626861A1 (de) | 2020-03-25 |
CN112912543B (zh) | 2023-05-05 |
WO2020057998A1 (de) | 2020-03-26 |
US20210348286A1 (en) | 2021-11-11 |
KR20210060468A (ko) | 2021-05-26 |
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