NL2033215B1 - Thin-film composite membrane for CO2 electrolysis - Google Patents
Thin-film composite membrane for CO2 electrolysis Download PDFInfo
- Publication number
- NL2033215B1 NL2033215B1 NL2033215A NL2033215A NL2033215B1 NL 2033215 B1 NL2033215 B1 NL 2033215B1 NL 2033215 A NL2033215 A NL 2033215A NL 2033215 A NL2033215 A NL 2033215A NL 2033215 B1 NL2033215 B1 NL 2033215B1
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- NL
- Netherlands
- Prior art keywords
- membrane
- thin film
- substrate
- electrolysis
- composite thin
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 139
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 60
- 239000010409 thin film Substances 0.000 title claims description 87
- 239000002131 composite material Substances 0.000 title claims description 80
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000012546 transfer Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 66
- 239000003792 electrolyte Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 230000007717 exclusion Effects 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 239000003011 anion exchange membrane Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 4
- 238000012695 Interfacial polymerization Methods 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 238000000909 electrodialysis Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229920009405 Polyvinylidenefluoride (PVDF) Film Polymers 0.000 claims 1
- 239000013626 chemical specie Substances 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000000108 ultra-filtration Methods 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 238000000502 dialysis Methods 0.000 abstract description 2
- 230000000116 mitigating effect Effects 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 107
- 239000000463 material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229960005419 nitrogen Drugs 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910021061 KOH 0.1M Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 230000008449 language Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable 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
- 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
- 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
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- 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
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- 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
- C25B3/26—Reduction of carbon dioxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08J2300/106—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is in the field of processes of separation using semi-permeable membranes, e.g., dialysis, osmosis, ultrafiltration, and an apparatus specially adapted therefor. It may also be considered to relate to a climate change mitigation technology in that carbon dioxide is con- verted by electrolysis to carbon comprising molecules, as well as to a technology for transfer of charged chemical species.
Description
Thin-film composite membrane for CO; electrolysis P100800NL00
The present invention 1s in the field of processes of separation using semi-permeable mem- branes, ¢.g. dialysis, osmosis, ultrafiltration, and an apparatus specially adapted therefor. It may also be considered to relate to a climate change mitigation technology in that carbon dioxide is converted by electrolysis to carbon comprising molecules, as well as to a technology for transfer of charged chemical species.
Electrolysis is a method using a direct electric current (DC) to drive an otherwise non-sponta- neous chemical reaction, converting first chemical species into further chemical species. Electroly- sis may be used in the separation of elements, such as from naturally occurring sources using an electrolytic cell. The voltage providing the direct electric current, needed for electrolysis to occur, is referred to as the decomposition potential. The word “electrolysis” finds its origin in the Greek lan- guage.
The main components involved in electrolysis are an electrolyte. a positive and a negative electrode, and an external power source providing the voltage and direct electric current. Typically a separator is present, such as an ion-exchange membrane, to prevent diffusion of species to the vicin- ity of the opposite electrode. The electrolyte is a chemical substance which contains free ions, and carries the electric current. Ions typically are mobile, in order for electrolysis to occur. A liquid electrolyte may be produced by solvation, bv reaction of an ionic compound with a solvent, and by melting of an 10nic compound. When immersed, in an example the electrodes are separated by a distance, such that a current flows between them through the electrolyte. They are connected to the external power source, which therewith completes the electrical circuit. Materials of which elec- trodes are formed are typically a metal, graphite, and a semiconductor material. Suitable electrodes may be selected in view of chemical reactivity between the electrode and electrolyte, and manufac- turing cost. Historically, graphite and platinum were often chosen.
A membrane is a selective barrier, allowing certain (chemical) species to pass through and preventing others from passing through. Membranes can be classified into synthetic membranes and biological membranes; the present invention relates to synthetic membranes. A first large scale use of membranes was in microfiltration and ultrafiltration technologies. A degree of selectivity of a membrane depends amongst others on the membrane pore size. Depending on the pore size, they can be classified as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmo- sis (RO) membranes. The present invention is in the field of NF and/or RO. Membranes can also be of various thickness, with homogeneous or heterogeneous structure. Membranes can be neutral or charged, and particle transport can be active or passive. The latter can be facilitated by pressure, concentration, chemical or electrical gradients of the membrane process. Important aspects of a membrane process operation relate to membrane permeability (k), operational driving force per unit membrane area and fouling and cleaning of the membrane surface.
A thin film is a layer of material with a thickness ranging from a monolayer to several mi- crometers. Thin films are typically deposited, such as on a substrate, typically under well-controlled 1 conditions. Upon deposition a controlled synthesis of materials forming the thin film occurs. A stack of thin films is called a multilayer. Deposition may take place using chemical [vapor] deposi- tion, physical [vapor] deposition, epitaxial growth mechanisms, atomic layer deposition, and so on.
Thin films find application in many fields of technology, ranging from batteries, to small apparat- uses, such as acoustic wave resonators, to coatings, and so on.
A research trend relates to the conversion of CO:. The electrochemical reduction or electro- catalytic conversion of CO: can produce value-added chemicals, such small alkanes as methane, small alkenes, such as ethvlene, small alcohols as ethanol, etc. The electrolysis of carbon dioxide can result in formate (COOH) or carbon monoxide, but sometimes more elaborate organic com- pounds such as ethylene. The technology is under research as a carbon-neutral route to organic compounds.
However the conversion of CO: is often not high enough, as often a high percentage of the input quantity of CO: is lost. Losses may be in the order of 40-60%. which makes processes uneco- nomical and difficult to maintain.
The present invention relates to an improved CO: conversion, which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages.
The present invention relates in a first aspect to a thin film composite membrane (TFCM) for CO: electrolysis (100), comprising a substrate, in particular a semipermeable membrane sub- strate, more in particular an ion exchange membrane substrate, preferably a high strength mem- brane, wherein the substrate is selected form an anion-exchange membrane substrate, a cation-ex- change membrane, and a bipolar membrane substrate, and on at least one side of the substrate, at least one polymeric film, in particular a dense polymeric film, more in particular with a size exclu- sion of < 1 nm as determined with size exclusion chromatography (Shimadzu LC-2010AHT, ISO 16014-1:2019), even more in particular with a size exclusion of < 0.5 nm, for example with a size exclusion of < 0.35 nm, in particular at least one first polymeric film on a first side of the substrate and at least one second polymeric film on a second side of the substrate. A film with such a size ex- clusion characteristics is considered to relate to a dense film. In the electrolysis CO: may be con- verted to CO, unsaturated or saturated C:-C: compounds, such as C=C, C;-C; alcohols, such as methanol, ethanol, propanol, butanol, and isopropanol. and C1-C: carboxylic acids, such as formic acid. acetic acid, propionic acid. and combinations thereof. For instance, formic acid may be formed in an electrolytic cell. wherein the cell operates at a current density of about 140 mA/cm? at a cell voltage of 3.5 V. Power consumption is in the order of 4.5 kWh/kg of product. For forming CO a cell has been operated at current densities of 200 to 600 mA/em? at about 3 V. The present compo- site membrane comprises a substrate. and at least one, typically one. thin film. The present thin film prevents carbonate (CO:”) and bicarbonate (HCO:’) from passing the membrane. The present membranes typically comprise a homogeneous structure, that is, with little or substantially no varia- tion in composition and structure. The present membrane composite is typically charged, though a net surface charge may still be substantially 0, that is, it comprises substantially the same amount of positive charge and negative charge. Chemical species transport over the composite membrane is 2 typically active, that is requiring a driving force, such as a pressure, a concentration difference, a voltage, or the like. Typically the present membrane is used in a cross-flow mode of operation. The present TFCM may be considered as a bi-functional membrane. It can be applied to solve critical problems with CO: electrolysis. It is noted that in prior art CO: electrolysis more than 50% of the
CO: input is lost, as CO: dissolves typically as bicarbonate. The present TFCM reduces losses of
CO: well below 50%, typically below 40%, such as to 1-30%, e.g. 53-20%, depending on the precise conditions. Therewith an alkaline anolyte medium, having a relatively high pH is now possible. In addition, the use of rather expensive catalysts. such as Ir, is also no longer required.
In a second aspect the present invention relates to a system for electrolysis comprising at least one first electrode of a first polarity, at least one second electrode of a second polarity, the second polarity being opposite of the first polarity, at least one first chamber comprising a first electrolyte, at least one second chamber comprising at least one second electrolyte, and at least one thin film composite membrane according to the invention, the membrane physically separating the first and second chamber, in particular wherein a volume of the respective at least one first chamber and the at least one second chamber each individually is from 1-2500 cm’, such as 10-1000 cm’.
In a third aspect the present invention relates to a method of converting COs, comprising providing a system according to the invention, providing CO: to the system. and converting CO: into a chemical compound selected from CO, unsaturated or saturated C,-C4 compounds, such as
C=C, C:-C: alcohols, and C;-C; carboxylic acids.
In a fourth aspect the present invention relates to a method of forming the thin film composite membrane according to the invention, comprising providing a substrate, in particular a membrane substrate, wherein the substrate is selected form an anion-exchange membrane substrate, and a bipo- lar membrane substrate, and providing at least one polymeric film on at least one side of the sub- strate by interfacial polvmerization, in particular a dense polymeric film, more in particular with a size exclusion of < 10 nm.
The present invention also relates to a use of a thin film composite membrane according to the invention or a system according to the invention, for transfer of charged chemical species, in particular charged chemical species selected from cations and anions, in particular for electrochemi- cal separation, for electrolysis, and for combinations thereof. Electrolysis may be performed in a fluid, such as a gas, in an aqueous environment, such as an aqueous electrolyte, in relatively pure conditions, such as an mainly aqueous electrolyte, or in more complex electrolytes, such as salty electrolytes, e.g. NaCl comprising electrolvte.
Thereby the present invention provides a solution to one or more of the above mentioned problems.
Advantages of the present description are detailed throughout the description. References to the figures are not limiting, and are only intended to guide the person skilled in the art through de- tails of the present invention.
The present invention relates in a first aspect to the thin film composite membrane ac- cording to claim 1. 3
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis the polymeric film has a thickness of 10-500 nm, in particular 50-300 nm, more in particu- lar 100-200 nm.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis the substrate is resistant to alkaline substances, in particular to OH’, more in particular re- sistant up to a temperature of 70 °C at a molar concentration of | mole/l during 24 hours.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolvsis the substrate is selective for bicarbonate, in particular wherein the substrate has a selectivity for OH" of >70%, in particular > 85%, more in particular > 95% (at 0 °C and 100 kPa, versus Hs).
In an exemplary embodiment of the present thin film composite membrane for CO; elec- trolysis the polvmeric film comprises surface charges, in particular with a surface charge density of > [1107 C/mm?| at a pH of 7, that is, when exposed to a neutral electrolyte or solution with a pH of about 7, in particular > |1*107* C/mm?, more in particular < |1¥10” C/mm?|.
In an exemplary embodiment of the present thin film composite membrane for CO; elec- trolysis a surface charge is selected from an anion, a cation, and combinations thereof.
In an exemplary embodiment of the present thin film composite membrane for CO; elec- trolysis a surface charge is selected from an anion, a cation, a localized charge, a partial charge, and combinations thereof.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis the substrate is at least partly formed of a chemical compound comprising at least one nitro- gen atom, in particular at least two nitrogen atoms, wherein the chemical compound is selected from saturated and unsaturated organic molecules.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolvsis the chemical compound is selected from 5-ring and 6-ring comprising molecules.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis the S-ring and 6-ring comprising molecules comprise at least one nitrogen, in particular at least two nitrogens, such as imidazole.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis the substrate has a thickness of 1-500 um, in particular 4-240 um, more in particular 12-120 um, even more in particular 20-60 um, such as 25-35 um.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolvsis the polymeric film is selected from a polyamide film, a polypropylene (PP) film, a Polyvi- nylidene fluoride (PVDF) film, a cellulose acetate film, in particular a Cellulose di(or trijacetate film, a Piperazine film, a graphene film, a Graphene oxide film, and a PTFE film.
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis a surface area of the thin film composite membrane is 1-10° em? in particular 2-10" cm? more in particular 10-10° em?
In an exemplary embodiment of the present thin film composite membrane for CO; elec- trolysis a ratio in permeance of OH versus the permeance of carbonate ions of the thin film compo- site membrane is larger than 5, in particular larger than 20. 4
In an exemplary embodiment of the present thin film composite membrane for CO: elec- trolysis wherein a ratio in permeance of H' versus the permeance of Na’ ions of the thin film com- posite membrane is larger than 5, in particular larger than 20 [under which conditions measured by applying a current for a period of time, measuring a concentration change, e.g. via pH/titration, and ion chromatography.
In an exemplary embodiment the present system comprises a catalyst, in particular an
Ag catalyst, or a Cu catalyst, more m particular wherein the catalyst is provided on the thin film composite membrane and in electrical and physical contact with the thin film composite membrane, such as by pressing.
In an exemplary embodiment of the present system the system is selected from a system wherein the first and second electrode are physically attached to the thin film composite membrane, and a system wherein the first and second electrode are physically separated from the thin film com- posite membrane.
In an exemplary embodiment of the present system the system a ratio of the combined first chamber and second chamber volume: the surface area of the thin film composite membrane is 102-10 em*:em?, in particular 107-2 cm®:ecm?, more in particular 107-1 cm*:cm?, even more in par- ticular 2*107-0.5 cm*:cm?.
In an exemplary embodiment of the present method in operation the pH of the at least one first chamber comprising an anolyte is 7.5-12, in particular 9-11, and/or wherein in operation the pH of the at least one second chamber comprising a catholyte is 4-7, in particular 5-6.
In an exemplary embodiment of the present method, in case of an anion exchange mem- brane, in operation the pH of the at least one first chamber comprising an anolyte is 7.5-14, in par- ticular 10-13.5, more in particular 11-12.
In an exemplary embodiment of the present method an Ag catalyst, or a Cu catalyst, is used.
In an exemplary embodiment of the present method conversion of CO: is provided at an operation energy of <3 kWh/kg of product, in particular <1 kWh/kg product, [current of <300 mA and voltage of 3V]
In an exemplary embodiment of the present method of forming the thin film composite membrane the substrate is an anion exchange membrane, and wherein the at least one polymeric film is a polyamide, and wherein the polymerization is by reacting m-phenylenediamine with 1,3,4- benzenetricarbonyl trichloride.
In an exemplary embodiment of the present method of forming the thin film composite membrane the reaction is carried out during 1-60 minutes, at a temperature of 20-80 °C, at a pres- sure of 90-110 kPa, at a concentration of 0.01-1 mol m-phenylenediamine, at a concentration of 0.01-1 mol 1,3.4-benzenetricarbonyl trichloride, and at a ratio of m-phenylenediamine : 1,3 4-ben- zenetricarbonyl trichloride of 0.5-2.
The present invention further relates to a use of a thin film composite membrane according to the invention, for transfer of charged chemical species. in particular selected from cations and ani- ons, in particular for electrochemical separation, such as wherein the use is in acid-base production, 5 in a flow battery, or in electrolysis.
The invention is further detailed by the accompanying figures and examples, which are exemplary and explanatory of nature and are not limiting the scope of the invention. To the person skilled in the art it may be clear that many variants, being obvious or not, may be conceivable falling within the scope of protection, defined by the present claims.
Figure 1a shows principles of a prior art redox flow battery.
Fig. 1b,2 and 3a.b, and 4 show schematics of a present flow cell; figs. 5 and 6 show experimental results.
100 redox flow battery 10 membrane 11 catholyte tank 12 anolyte tank 13 contact (current collector) 14 pump 15 current flow 16 first chamber 17 second chamber 18 third chamber 31 first electrolyte flow 32 second electrolyte flow 40 thin film
Figure la shows principles of a prior art redox flow battery. Therein a single cell is shown.
The cell comprises a membrane 10, and contacts 13 (current collector). Also a catholyte tank 11 and an anolyte tank 12 is shown. Two pumps 14 are provided for driving a flow; a first electrolyte flow 31 and a second electrolyte flow 32 is shown. As a result an electrical current 15 flows. Also first and second chambers 16,17 are shown.
Figure 1b shows a similar layout as fig. la, only the current flows from membrane 10 to a contact 13.
In a similar manner fig. 2 shows schematically the functioning of the present flow cell, com- prising two catholyte tanks, and an extra chamber 18, parallel to chamber 16. Such may be in partic- ular relevant if a first tank 11 comprises a liquid. and a second tank 11 comprises a gas. The separa- tor 13 may be a gas diffusion electrode. The figures are further detailed in the description of the ex- periments below.
In fig. 3a it is shown that a contact 13 and a membrane 10 are physically separated by a respective first chamber 16 and second chamber 17, whereas in fig. 3b the contacts 13 are in physical contact with membrane 10, and first chamber 16 and second chamber 17 are on opposite sides of the con- tact/membrane/contact stack. 6
Fig. 4 shows a membrane with a thin film, forming the present thin film composite mem- brane.
Figure 5 - Transport numbers of OH- and CO32- under a stable current. M_ Base is the bare
AEM and M1-M4 are different tested TFCMs.
Figure 6 - Products at the anode side of a CO2 electrolyzer employing a TFCM.
EXAMPLES/EXPERIMENTS
Selectivity to OH vs CO:”
Figure 5 shows the result of the cross-over experiments of hydroxide vs carbonate, be- fore optimization of the coating process. However, it can already be observed that the transport number of OH has a clear increase for the modified membranes. Since CO5* carries twice the charge of OH’, it is concluded that at least 85 % of the ions crossing over the modified mem- branes were OH in this experiment.
After optimizing reagent concentrations, drying time and ensuring a uniform film, the ionic resistance of a non-coated AEM and that of a TFCM were measured in 0.1 M KOH and
K;C0:. The table shows that the coating gives a very low increase in terms of resistance to- wards OH" but the resistance in carbonate has increased at least 22-fold.
Table 1 - Ionic resistance measured in a 6 compartment setup with 4 electrode configuration.
Ionic Resistance (Q.cm2) 0.1M KOH 0.1M K;CO0:
AEM 4.52 +0.02 5.59 + 0.07
TFCM 4.89 + 0.01 >110%* * very low limiting current
Furthermore, the TFCM was tested in a CO: electrolyzer. Carbonate cross-over toward the anolyte is a major issue in prior art CO: electrolysis, since there it oxidizes back to COs.
This leads to a loss of around 50% of the reagent, making the prior art process inefficient and less economically viable. It has been shown in literature that during stable operation, the molar ratio of CO: to O; gas produced at the anode is 2:1. Figure 6 shows the gasses produced at the anode side in our experiment using a TFCM (02 left lower points, right higher points; arrow).
It can be observed, that there is a low amount of CO: produced that is independent of current density. If this CO: was due to carbonate cross-over it would increase with current density. therefore it can be concluded that is not its origin. It can be due to the pre-column of the gas chromatograph for example. Meaning, our TFCM allows little to no cross-over of carbonate during operation.
Stability of the polvamide films
Long term operation tests and analysis after exposure to different solutions are still re- quired to confirm the stability of these films.
In terms of delamination, we believe that the film will be extremely stable since the PA film is entangled in the polymeric structure of the AEM. Firstly. because in order to create this film using interfacial polymerization, we let the water phase soak the membrane, and then 7 completely remove the excess from the top, until the membrane appears almost dry. Only then is the organic phase with the second monomer added, meaning the interface where the polymerization happens is the surface of the AEM. Secondly, the XPS analysis (Table 2) in the first 10 nm of the sample, already shows a low amount of a different NH» structure (NH»*) from the one of the PA films. These amines correspond to the immobilized amine groups of the AEM. And it is known from literature (refs) that the PA films created with this concentra- tion of reagents have a thickness of 100 to 200 nm. Meaning, the majority of the film is within the polymeric structure of the AEM. The XPS analysis also confirms the film's atomic struc- ture is consistent with literature (Table 3).
Table 2 - XPS results for 10 nm depth of a polyamide film. Analysis of states of NH: present. NH2* denominates a different state of NH,.
Sample Name Position “At Conc
TFCM1 001 NH: 399.98 97.21
NH;* 402.43 2.79
TFCM1 002 NH: 399.97 90.64
NH;* 402.49 9.36
TFCMI 003 NH: 399.91 87.47
NH:* 402.48 12.53
Table 3 - XPS results for 10 nm depth of a polyamide film. Percentages of C, N and O atoms.
CNO, atomic % C. aver % N, aver % 0, aver %
TFCM1 75.1 7 15.0 deviation 0.7 1 0.1
In terms of chemical stability, RO membranes have been optimized to work for quite a wide range of feeding solutions. There is a vast choice of materials which can be used for different applications, so it is a matter of finding the correct material, among the already avail- able ones.
The invention although described in detailed explanatory context may be best under- stood in conjunction with the accompanying figures.
It should be appreciated that for commercial application it may be preferable to use one or more variations of the present system, which would similar be to the ones disclosed in the present application and are within the spirit of the invention.
For the sake of searching the following section is added reflecting embodiments of the pre- sent invention and which represents a translation of the subsequent section. 1. A thin film composite bifunctional membrane for CO: electrolysis (100), comprising a substrate, in particular a semipermeable membrane substrate, more in particular an ion ex- change membrane substrate, preferably a high strength membrane, wherein the substrate 1s selected form an anion-exchange membrane substrate, a cation-exchange membrane, and a bipolar mem- brane substrate. and on at least one side of the substrate, at least one polymeric film, in particular a dense polymeric film, more in particular with a 8 size exclusion of < 1 nm as determined with size exclusion chromatography (Shimadzu LC- 2010AHT ISO 16014-1:2019), even more in particular with a size exclusion of < 0.5 nm, for exam- ple with a size exclusion of < 0.35 nm, in particular at least one first polymeric film on a first side of the substrate and at least one second polymeric film on a second side of the substrate. 2. The thin film composite membrane for CO: electrolysis according to embodiment 1, wherein the polymeric film has a thickness of 10-500 nm, in particular 50-300 nm, more in particular 100-200 nm, 3. The thin film composite membrane for CO: electrolysis according to any of embodiments 1-2, wherein the substrate is resistant to alkaline substances, in particular to OH’, more in particular re- sistant up to a temperature of 70 °C at a molar concentration of 1 mole/I during 24 hours. 4. The thin film composite membrane for CO: electrolysis according to any of embodiments 1-3, wherein the substrate is selective for bicarbonate, in particular wherein the substrate has a selectiv- ity for OH of 70%, in particular > 85%, more in particular > 95% 5. The thin film composite membrane for CO; electrolysis according to any of embodiments 1-4, wherein the polymeric film comprises surface charges, in particular with a surface charge density of > [1*1075 C/mm? at a pH of 7, in particular > [1¥ 10° C/mm?|, more in particular <|1*10” C/mm?, and/or wherein a surface charge is selected from an anion, a cation, a localized charge, a partial charge, and combinations thereof. 6. The thin film composite membrane for CO: electrolysis according to any of embodiments 1-5, wherein the substrate at least partly comprises a chemical compound comprising at least one nitro- gen atom, in particular at least two nitrogen atoms, wherein the chemical compound is selected from saturated and unsaturated organic molecules, and/or wherein the chemical compound is selected from 5-ring and 6-ring comprising molecules. 7. The thin film composite membrane for CO; electrolysis according to embodiment 6, wherein the
S-ring and 6-ring comprising molecules comprise at least one nitrogen, in particular at least two ni- trogens, such as imidazole. 8. The thin film composite membrane for CO: electrolysis according to any of embodiments 1-7, wherein the substrate has a thickness of 1-500 um, in particular 4-240 um, more in particular 12- 120 pm, even more in particular 20-60 um. such as 25-35 um. 9. The thin film composite membrane for CO; electrolysis according to any of embodiments 1-8, wherein the polymeric film is selected from a polvamide film, a polypropylene (PP) film, a Polvvi- nylidene fluoride (PVDF) film, a cellulose acetate film, in particular a Cellulose di(or trijacetate film, a Piperazine film, a graphene film, a Graphene oxide film, and a PTFE film. 10. The thin film composite membrane for CO: electrolysis according to any of embodiments 1-9, wherein a surface area of the thin film composite membrane is 1-10° cm?, in particular 2-10* cm. 11. The thin film composite membrane for CO: electrolysis according to any of embodiments 1-10, wherein a ratio in permeance of OH versus the permeance of carbonate ions of the thin film compo- site membrane is larger than 5, in particular larger than 20, and/or wherein a ratio in permeance of H* versus the permeance of Na” ions of the thin film composite 9 membrane is larger than 5. in particular larger than 20. 12. System for electrolysis comprising at least one first electrode of a first polarity, at least one second electrode of a second polarity, the second polarity being opposite of the first po- larity, at least one first chamber comprising at least one first electrolyte, at least one second chamber comprising at least one second electrolyte, and at least one thin film composite membrane according to any of embodiments 1-11, the membrane physically separating the first and second chamber, in particular wherein a volume of the respective at least one first chamber and the at least one sec- ond chamber each individually is from 1-2500 em’, such as 10-1000 cm’. 13. The system according to embodiment 12, comprising a catalyst, in particular an Ag catalyst, or a Cu catalyst, more in particular wherein the catalyst is provided on the thin film composite membrane and in electrical and physical contact with the thin film composite membrane, such as by pressing. 14. System according to any of embodiments 12-13, wherein the system is selected from a system wherein the first and second electrode are physically attached to the thin film composite membrane, and a system wherein the first and second electrode are physically separated from the thin film com- posite membrane. 15. System according to any of embodiments 12-14, wherein a ratio of the combined first chamber and second chamber volume: the surface area of the thin film composite membrane is 10-10 cm*:cm?, in particular 102-2 em*:cm?, more in particular 107-1 cm*:em?, even more in particular 2*107-0.5 cm’:em”. 16. A method of converting CO, comprising providing a system according to any of embodiments 12-15, providing CO: to the system, and converting CO: into a chemical compound selected from CO, unsaturated or saturated C1-C4 com- pounds, such as C=C, C:1-C: alcohols, and C1-C4 carboxylic acids. 17. The method of converting CO; according to embodiment 16, wherein in operation the pH of the at least one first chamber comprising an anolyte is 7.5-12, in particular 9-11, and/or wherein in op- eration the pH of the at least one second chamber comprising a catholyte is 4-7, in particular 5-6. 18. The method of converting CO; according to embodiment 16 or 17, in case of an anion exchange membrane, wherein in operation the pH of the at least one first chamber comprising an anolyte is 7.5-14, in particular 12-13.5. 19. The method of converting CO; according to any of embodiments 16-18, wherein an Ag catalyst, or a Cu catalyst, is used. 20. The method of converting CO; according to any of embodiments 16-19, wherein conversion of
CO: is provided at an operation energy of <3 kWh/kg of product, in particular <1 kWh/kg product. in particular at a current of <300 mA and a voltage of 3V. 21. Method of forming the thin film composite membrane according to any of embodiments 1-11, 10 comprising providing a substrate, in particular a semipermeable membrane substrate, more in particular an elec- trodialysis membrane substrate, wherein the substrate is selected form an anion-exchange mem- brane substrate, and a bipolar membrane substrate, and providing at least one polymeric film on at least one side of the substrate by interfacial polymeriza- tion, in particular a dense polymeric film, more in particular with a size exclusion of < 10 nm. 22. Method according to embodiment 21, wherein the substrate is an anion exchange membrane, and wherein the at least one polymeric film is a polyamide, and wherein the polymerization is by reacting m-phenylenediamine with 1,3.4-benzenetricarbonyl trichloride.
23. Method according to embodiment 22, wherein the reaction is carried out during 1-60 minutes, at a temperature of 20-80 °C, at a pressure of 90-110 kPa, at a concentration of 0.01-1 mol m-phe- nylenediamine, at a concentration of 0.01-1 mol 1,3,4-benzenetricarbonyl trichloride, and at a ratio of m-phenylenediamine : 1,3.4-benzenetricarbonyl trichloride of 0.5-2.
24. Use of a thin film composite membrane according to any of embodiments 1-11 or a system ac-
cording to embodiments 12-15, for transfer of charged chemical species, in particular charged chemical species selected from cations and anions, in particular for electrochemical separation, for electrolysis, such as an aqueous electrolyte, and for combinations thereof.
25. Use of a thin film composite membrane according to embodiment 24, wherein the use is in acid- base production, in a flow battery. or in electrolysis.
11
Claims (25)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954388A (en) * | 1988-11-30 | 1990-09-04 | Mallouk Robert S | Fabric reinforced composite membrane |
| AU2020393869A1 (en) * | 2019-11-25 | 2022-06-09 | Twelve Benefit Corporation | Membrane electrode assembly for COx reduction |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954388A (en) * | 1988-11-30 | 1990-09-04 | Mallouk Robert S | Fabric reinforced composite membrane |
| AU2020393869A1 (en) * | 2019-11-25 | 2022-06-09 | Twelve Benefit Corporation | Membrane electrode assembly for COx reduction |
Non-Patent Citations (3)
| Title |
|---|
| CHARLES DELACOURT ET AL: "Design of an Electrochemical Cell Making Syngas (CO+H2) from CO2 and H2O Reduction at Room Temperature", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 155, no. 1, 1 January 2008 (2008-01-01), pages B42, XP055124598, ISSN: 0013-4651, DOI: 10.1149/1.2801871 * |
| PETROV KOSTADIN V. ET AL: "Anion-exchange membranes with internal microchannels for water control in CO2 electrolysis", SUSTAINABLE ENERGY FUELS, no. 6, 28 September 2022 (2022-09-28), pages 5077 - 5088, XP093050250 * |
| YAN ZHIFEI ET AL: "Improving the efficiency of CO2 electrolysis by using a bipolar membrane with a weak-acid cation exchange layer", NATURE CHEMISTRY, vol. 13, no. 1, January 2021 (2021-01-01), pages 33 - 40, XP037320731, ISSN: 1755-4330, DOI: 10.1038/S41557-020-00602-0 * |
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