WO2023220520A1 - Mode de fonctionnement d'électrolyse du dioxyde de carbone - Google Patents
Mode de fonctionnement d'électrolyse du dioxyde de carbone Download PDFInfo
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- WO2023220520A1 WO2023220520A1 PCT/US2023/066147 US2023066147W WO2023220520A1 WO 2023220520 A1 WO2023220520 A1 WO 2023220520A1 US 2023066147 W US2023066147 W US 2023066147W WO 2023220520 A1 WO2023220520 A1 WO 2023220520A1
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- Prior art keywords
- co2rr
- pressure
- phase boundary
- electrochemical cell
- cathode
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 97
- 239000001569 carbon dioxide Substances 0.000 title description 49
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 49
- 238000005868 electrolysis reaction Methods 0.000 title description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 46
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000011949 solid catalyst Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 3
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- 239000000470 constituent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
-
- 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
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
- C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
-
- 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
-
- 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
Definitions
- the present invention relates in general to a carbon dioxide (CO2) electrolysis operation mode, and more specifically to an improved CO2 reduction reaction (CO2RR) utilizing back pressure, and most specifically to a CO2RR electrochemical cell operation mode utilizing back pressure.
- CO2RR CO2 reduction reaction
- CO2RR has many beneficial aspects.
- One aspect involves the clean generation of reaction products, such as hydrocarbons, alcohols, H2 and/or CO, that then can be used to feed any of a variety of industrial, commercial, individual or common inputs such as factories, gas turbines, equipment, vehicles, etc., as well as repositories and other storage mediums, as well as ambient or polluted air.
- Another aspect involves the consumption or destruction of greenhouse gas CO2, such as from CO2 emitting industrial, commercial, individual or common sources such as factories, gas turbines, equipment, vehicles, etc., as well as repositories and other storage mediums, as well as ambient or polluted air.
- Yet another aspect involves integration of CO2RR with renewable energy sources such as solar, wind, geothermal, etc., whereby the renewable energy sources provide the requisite electricity or E o to initiate or sustain the CO2RR.
- Still another aspect involves combinations of two or more the above aspects, such as consuming CO2 flue gas from a factory source while sustaining the CO2RR from electricity generated from solar panels on the factory roof and then storing or feeding the produced value-added reaction product, such as ethene or higher order hydrocarbons, for a desired use.
- CO2RR, electrochemical cell and operation mode problems may include CO2 reaction inefficiency and instability overtime. Some efforts to overcome these problems involve modifying the catalyst surface such that the CO2 and its intermediary reactants are more strongly bounded on the catalyst. Other efforts to overcome these problems involve modifying the cathode to optimize gas diffusivity, porosity, thickness, hydrophilicity, electrical conductivity, ionic conductivity, wettability, etc. However, there remains a need for an improved CO2RR, electrochemical cell and/or operation mode and a particular need for an easily implemented, inexpensive and industrial scalable improved CO2RR, electrochemical cell, and/or operation mode. [0014]
- a CO2RR 2 comprising a three- phase boundary 14 having: a gaseous CO2 diffused at least partially through a porous cathode 8, a solid catalyst 10 operatively associated with the cathode 8, and a catholyte 12 or membrane 16 in communication with the catalyst 10; a pressure controller 30 adapted to control the pressure in gas chamber 6 and consequently the back pressure (pressure difference between the gas feed chamber 6 and the catholyte chamber 12) within, at or near the three-phase boundary 14; and a reaction product of the CO2RR such as but not limited to hydrocarbons, alcohols, H2 and/or CO.
- an electrochemical cell 2 comprising: an inlet 4 through which gaseous CO2 enters the electrochemical cell 2 and advances into a chamber 6; a porous cathode 8 through which the gaseous CO2 in the chamber 6 can at least partially diffuse through; a solid catalyst 10 adhered to the cathode 8; a liquid catholyte 12 in fluid communication with the solid catalyst 10, wherein the gaseous CO2 contained in the porous cathode 8 and the solid catalyst 10 and the liquid catholyte 12 collectively form a three-phase boundary 14; a membrane 16 that separates the cathode 8 from an anode 20 to prevent short circuiting of the electrochemical cell 2 while allowing cations to circulate between the liquid catholyte 12 and a liquid anolyte 18; an outlet 22 through which reaction product(s) of the CO2RR exits the electrochemical cell 2; a pressure sensor 24 arranged within, at or near the three-phase boundary 14 to detect the pressure
- a, CO2RR 2 comprising a three-phase boundary 14 having: a gaseous CO2 diffused at least partially through a porous cathode 8, a solid catalyst 10 operatively associated with the cathode 8, and a liquid catholyte 12 or membrane 16 in communication with the catalyst 10; a pressure controller 30 that controls the pressure within the three-phase boundary 14 in order to increase a dwell time of the CO2RR 2 within the three-phase boundary 14; and a reaction product of the CO2RR such as but not limited to hydrocarbons, alcohols, H2 and/or CO.
- an electrochemical cell 2 comprising: an inlet 4 through which gaseous CO2 enters the electrochemical cell 2 and advances into a chamber 6; a porous cathode 8 through which the gaseous CO2 in the chamber 6 can at least partially diffuse through; a solid catalyst 10 adhered to the cathode 8; a liquid catholyte 12 in fluid communication with the solid catalyst 10, wherein the gaseous CO2 contained in the porous cathode 8 and the solid catalyst 10 and the liquid catholyte 12 collectively form a three-phase boundary 14; a membrane 16 that separates the cathode 8 from an anode 20 to prevent short circuiting of the electrochemical cell 2 while allowing cations to circulate between the liquid catholyte 12 and a liquid anolyte 18; an outlet 22 through which reaction product(s) of the CO2RR exits the electrochemical cell 2; pressure sensors 24, 26 arranged near the three-phase boundary 14 to detect the pressure within the three phase boundary
- FIG 1 is a detail view of a CO2RR three phase boundary utilizing back pressure in accordance with an exemplary embodiment of the subject matter.
- FIG 2 is a schematic of a CO2RR electrochemical cell operation mode utilizing back pressure in accordance with an exemplary embodiment of the subject matter.
- a CO2RR utilizing back pressure to control CO2 dwell or occupation within, at or near a three-phase boundary and thereby control the CO2RR and desired reaction produces) is provided.
- the illustrated three-phase boundary comprises a gaseous CO2 diffused at least partially through a porous cathode 8, a solid catalyst 10 operatively associated with the porous cathode 8, and a liquid (or solid polymer) catholyte 12 or membrane 16 in communication with the catalyst 10.
- Establishing a back pressure, at or near the three-phase boundary 14 to 0 - 400 mbar and preferably to 30- 130 mbar is particularly suited for the efficient generation of hydrocarbon product(s).
- Reaction products may include hydrocarbons (of either or both higher and lower order), alcohols, H2 and/or CO. If no catholyte 12 is used, the catholyte 12 alkaline environment functionality may be achieved by membrane 16. Also in this catholyte-less configuration, the three- phase boundary 14 becomes the cathode 8, catalyst 10 and membrane 16, with membrane 16 liquidity source-able from the liquid anolyte 18 or other suitable liquid source associated with the cell 2. [0025] As illustrated in Figure 2, an operation mode utilizing back pressure on a CO2RR electrochemical cell 2 is also provided.
- the illustrated electrochemical cell 2 comprises a CO2 inlet 4, a three-phase boundary 14 comprising a porous cathode 8 through which gaseous CO2 is diffused, a solid catalyst 10 adhered to the cathode 8, a liquid catholyte 12 in fluid communication with the catalyst 10, as well as a membrane 16 that separates the cathode 8 from an anode 20 2 while allowing cations to circulate between the liquid catholyte 12 and a liquid analyte 18, along with a reaction product outlet 22.
- a pressure sensor 24 is arranged within, at or near the three-phase boundary 14 to detect the pressure in catholyte chamber 12 within, at or near the three-phase boundary 14.
- a pressure controller 30 is adapted to control the pressure in gas chamber 6 and consequently the pressure difference (back pressure) between gas chamber 6 and catholyte chamber 12.
- the pressure controller 30 maintains a pressure difference of 0 - 400 mbar and preferably 30 - 130 mbar between gas chamber 6 and catholyte chamber 12.
- a pressure difference 0 - 400 mbar and preferably 30 - 130 mbar between gas chamber 6 and catholyte chamber 12.
- gas diffusion layer constitution and operation conditions including applied current density, temperature, flow rates and the like, not all of the elements shown in Figure 2 are necessary to provide a CO2RR electrochemical cell 2 operation mode utilizing back pressure in order to generate CO2RR products.
- the electrochemical cell 2 has a CO2 inlet 4 configured to receive CO2 gas from any one or more of a variety of CO2 sources, including without limitation, industrial, commercial, individual or common sources such as factories, gas turbines, equipment, vehicles, etc., as well as repositories and other storage mediums, as well as ambient or polluted air.
- the CO2 optionally may be conditioned before, within or after the inlet 4, such as by humidification via H2O or other suitable means.
- Figure 1 exemplarily illustrates humidified CO2 passing through the inlet 4 into a chamber 6 that holds and allows dispersion of the CO2.
- no or more than one inlet 4 and no or more than one chamber 12 can be used, and any inlet(s) 4 and chamber(s) 6 used can be arranged at different location(s) on, along, or through the electrochemical cell 2.
- a porous cathode 8 is arranged to receive the gaseous CO2 and configured such that the CO2 can diffuse through at least a portion of the cathode 8.
- the exemplarily illustrated cathode 8 is a gas diffusion electrode (GDE) that absorbs and converts the CO2 molecules into the desired CO2RR reaction product e.g. hydrocarbons, however other suitable cathodes 8 could be used.
- GDE gas diffusion electrode
- a solid catalyst 10 is operatively associated with the cathode 8 by any suitable means, such as drop casting, plating, doping, or spray coating to enhance reaction product selectivity as well as reaction efficiency and stability. Suitable catalysts 10 include but are not limited to Pt, Zn, Cu, Ag, Au, Pd and Sn. Since Cu is the only transition metal catalyst for CO2RR to value added C2+ reaction products e.g. ethene, ethanol, propanol, Cu is therefore preferred but not required when desiring those reaction products.
- a catholyte 12 is advantageously arranged in communication with the catalyst 10 to provide an alkaline environment close to the three-phase boundary 14 and thereby promoting CO2RR thermodynamically and kinetically when hydrocarbon reaction product(s) and/or a CO reaction product is desired.
- the exemplarily illustrated catholyte 12 is an alkaline buffer liquid solution, such as potassium hydrogen carbonate, cesium hydrogen carbonate, rubidium hydrogen carbonate, lithium bicarbonate or potassium hydroxide, but the catholyte 12 may also be embodied as a solid polymer.
- a three-phase boundary 14 is thereby formed by: (1) the gaseous CO2 diffused at least partially through the cathode 8, (2) the solid catalyst 10 operatively associated with the cathode 8, and (3) the liquid (or solid polymer) catholyte 12 in communication with the catalyst 10.
- Figure 1 provides a detailed illustration of the three- phase boundary, exemplary H+ and CO2 reaction constituents, as well as exemplary desired and undesired CO2RR reaction products.
- a membrane 16 optionally may be used to separate the cathode 8 from an anode 20 while allowing cations to circulate between the liquid catholyte 12 and a liquid anolyte 18.
- exemplary suitable membranes 16 include sulfonated tetrafluoroethylene based fluoropolymer-copolymer (Nafion). If used, the anolyte 18 is advantageously an alkaline buffer solution to complete the ion circuitry of the electrochemical cell 2.
- Exemplary suitable analytes 18 include H2O, OH-, H + and electrolyte associated cations and anions (e.g. Cs” and SOfi 2 ).
- the anode 60 material can be composed of Ir, Ni and/or Pt, where the anode would be responsible for O2 evolving reaction and completing the ion circuit in the electrochemical cell by pumping H + to the cathode.
- the membrane 16 preferably an anion exchange membrane 16 or a bipolar membrane 16 may be used to sustain the alkaline environment rather than or in addition to the catholyte 12.
- the membrane 16 preferably an anion exchange membrane 16 or a bipolar membrane 16
- the membrane 16 may be used to sustain the alkaline environment rather than or in addition to the catholyte 12.
- the three-phase boundary 14 becomes the cathode 8, catalyst 10 and membrane 16, with membrane 16 liquidity source-able from the liquid anolyte 18 or other suitable liquid source associated with the cell 2.
- a reaction product outlet 22 is configured to receive the reaction product, e.g. hydrocarbon gas, from the electrochemical cell 2 and feed the reaction product to any one or more use sources, including without limitation, industrial, commercial, individual or common sources such as factories, gas turbines, equipment, vehicles, etc., as well as repositories and other storage mediums, as well as ambient or polluted air.
- the CO2 reaction product optionally may be conditioned before, within or after the outlet 22, such as by liquifying (e.g. to form LNG particularly if methane is a reaction product). Unconditioned reaction products are exemplary shown as passing through the outlet 22.
- no or more than one outlet 22 can be used, and any outlet(s) 22 used can be arranged at different location(s) on, along, or through the electrochemical cell 2.
- a pressure sensor 24 is arranged in operative communication with the electrochemical cell 2 in order to detect pressure in catholyte chamber 12 within, at or near the three-phase boundary 14.
- the exemplary embodiment shows the pressure sensor 24 arranged near the three-phase boundary 14, toward the middle of the catholyte 12 between the cathode 8 and membrane 16, however, depending on the desired reaction product(s), electrochemical cell 2 configuration, three-phase boundary 14 constituents, or a variety of other factors, the pressure sensor 24 may be arranged in any of a variety of locations within, at or near the three-phase boundary 14. Also, if the three- phase boundary 14 is expansive or geometrically complex, then pressure sensors 26, 28 advantageously may be used to better sense the three-phase boundary 14 pressure and control the CO2RR.
- An outlet pressure sensor 26 may be advantageously arranged within, at or near the outlet 22 in order to detect pressure within, at or near the outlet 22.
- the exemplary illustration shows an outlet pressure sensor 26 arranged at the beginning of the outlet 22.
- one or more optional outlet pressure sensors 26 could be arranged in any of a variety of locations within, at or near the outlet 22 to better sense the outlet pressure and control the CO2RR.
- an inlet pressure sensor 28 may be arranged within, at or near the inlet 4 in order to detect CO2 pressure within, at or near the inlet 4.
- the exemplary illustration shows an optional inlet pressure sensor 28 arranged at the end of the inlet 4.
- one or more optional outlet pressure sensors 28 could be arranged in any of a variety of locations within, at or near the inlet 4 to better sense the inlet pressure and control the CO2RR.
- a pressure controller 30 is arranged in operative communication with the pressure sensor(s) 24, 26 and/or optional pressure sensor 28 and is adapted to adjust pressure detected by the pressure sensor(s) 24, 26 and/or optional pressure sensor 28 in order to adjust the back pressure within, at or near the three phase boundary 14 and/or outlet 22 or inlet 4.
- the exemplary illustration shows the pressure controller 30 located downstream of the outlet 22 and outlet pressure sensor 26 and embodied as a membrane valve with a flexible diaphragm that allows outlet flow only at, above, below or between a desired pressure.
- the pressure controller 30 may be embodied through any of a variety of suitable mechanisms and may be arranged in any of a variety of locations. Also, if the electrochemical cell 2, CO2 feed source, or reaction product feed use is expansive or complex, then additional pressure sensors 30 may be advantageously used to better control and control the CO2RR.
- FIG. 2 an exemplary illustration of CO2RR electrochemical cell 2 operation mode utilizing back pressure is provided.
- the CO2 is urged toward cathode 8 and diffuses through at least a portion of cathode 8, thereby contacting catalyst 10.
- the CO2RR thereby occurs within, at or near the three-phase boundary 14, with the reaction product then advancing through the outlet 22 for desired collection or use.
- Reaction product selectivity, as well as efficiency and stability, is improved by controlling the CO2 pressure within, at or near the three-phase boundary 14.
- One way to control the CO2 pressure within, at or near the three-phase boundary 14 is via the pressure controller 30 arranged in operative communication with the pressure sensor(s) 24 and 26, and/or optional pressure sensor 28 to thereby adjust pressures detected by the pressure sensor(s) 24 and 26, and/or optional pressure sensor 28 in order to adjust the back pressure within, at or near the three-phase boundary 14 and/or outlet 22 or inlet 4.
- CO2 inlet 4 pressure (Pl) is sensed as atmospheric at 1 mbar (within an exemplary preferred range of 0 mbar to 10 mbar), while three-phase boundary 14 pressure (P2) is sensed at 20 mbar (outside an exemplary preferred range of 30 mbar to 130 mbar).
- the three-phase boundary 14 pressure (P2) is adjusted to a pressure of 85 mbar (or anywhere within the exemplary preferred range of 30 mbar to 130 mbar) in order to better control the CO2RR and desired reaction product.
- CO2 outlet 22 pressure (P3) is 15 mbar (within an exemplary preferred range of 10 mbar to 30 mbar), while three-phase boundary 14 pressure (P2) varies between 120-150 mbar (partially within and partially outside an exemplary preferred range of 30 mbar to 130 mbar).
- the three-phase boundary 14 pressure (P2) is continually adjusted to a desired set pressure of 70 mbar (or anywhere within the exemplary preferred range of 30 mbar and 130 mbar) in order to better control the CO2RR and desired reaction products.
- CO2 inlet 4 pressure is 2-4 mbar as continually measured by inlet pressure sensor 28, while three-phase boundary 14 pressure (P2) is 60-75 mbar as continually measures by pressure sensor 24, and outlet 22 pressure (P3) is 5-10 mbar as continually measured by outlet pressure sensor 26.
- controller 30 Based on the P3, P2 and Pl pressure differences, as well as an exemplarily desired three-phase boundary 14 pressure range of 0 - 400 mbar (P3), an exemplarily desired inlet 4 pressure of 1 mbar (Pl) and an exemplarily desired outlet 22 pressure range of 2-5 mbar (P3), controller 30 periodically adjusts the three-phase boundary 14 pressure (P2) to 55 mbar (or anywhere between 0 mbar and 400 mbar), the inlet 4 pressure (Pl) to 1 mbar and the outlet 22 pressure (P3) to 4 mbar, in order to better control the CO2RR and desired reaction products.
- CO2 inlet 4 pressure is 50-75 mbar as continually measured by inlet pressure sensor 28, while three-phase boundary 14 pressure (P2) is 150-180 mbar as continually measures by pressure sensor 24, and outlet 22 pressure (P3) is 250-270 mbar as continually measured by outlet pressure sensor 26.
- controller 30 Based on the P3, P2 and Pl pressure differences, as well as an exemplarily desired three- phase boundary 14 pressure range of 0-400 mbar (P3), an exemplarily desired inlet 4 pressure of 75-100 mbar (Pl) and an exemplarily desired outlet 22 pressure range of 300- 320 mbar (P3), controller 30 periodically adjusts the three-phase boundary 14 pressure (P2) to 175 mbar (or anywhere between 80-100), the inlet 4 pressure (Pl) to 100 mbar and the outlet 22 pressure (P3) to 250 mbar, in order to better control the CO2RR and desired reaction products.
- P3 three-phase boundary 14 pressure
- a plurality of inlet pressure sensors 28 are employed near inlet 4 from which an average pressure (Pl) of 2 mbar is calculated, while a plurality of outlet pressure sensors 26 are employed near outlet 22 from which an average pressure (P3) of 10 mbar is calculated.
- controller 30 Based on the P3 and Pl pressure difference, as well as an exemplarily desired three-phase boundary 14 pressure range of 30 - 130 mbar, an exemplarily desired inlet pressure (Pl) of 1 mbar and an exemplarily desired outlet pressure range (P3) of 2-5 mbar, controller 30 adjusts the inlet pressure (Pl) to 1 mbar and the outlet pressure (P3) to 3 mbar, in order to better control the CO2RR and desired reaction products.
- pressure sensor 24 is not used while pressure sensors 26 and 28 are used.
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Metallurgy (AREA)
- Analytical Chemistry (AREA)
- Automation & Control Theory (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
L'invention concerne un CO2RR et une cellule électrochimique à CO2RR (2) comprenant une frontière triphasique (14) ayant : du CO2 gazeux diffusé au moins partiellement à travers une cathode poreuse (8), un catalyseur solide (10) associé de manière fonctionnelle à la cathode (8), et un catholyte (12) ou une membrane (16) en communication avec le catalyseur (10); un dispositif de commande de pression (30) conçu pour commander la contre-pression à l'intérieur, au niveau ou à proximité de la frontière triphasique (14); et un produit de réaction du CO2RR choisi dans le groupe constitué par : un hydrocarbure, un alcool, H2 et CO.
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EP22172254.9A EP4276223A1 (fr) | 2022-05-09 | 2022-05-09 | Mode de fonctionnement d'électrolyse de dioxyde de carbone |
EP22172254.9 | 2022-05-09 |
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WO2023220520A1 true WO2023220520A1 (fr) | 2023-11-16 |
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PCT/US2023/066147 WO2023220520A1 (fr) | 2022-05-09 | 2023-04-25 | Mode de fonctionnement d'électrolyse du dioxyde de carbone |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190233957A1 (en) * | 2016-06-30 | 2019-08-01 | Siemens Aktiengesellschaft | Arrangement for the Electrolysis of Carbon Dioxide |
WO2021023435A1 (fr) * | 2019-08-08 | 2021-02-11 | Siemens Aktiengesellschaft | Procédé de conversion électrochimique d'un gaz de départ au niveau d'une électrode de diffusion de gaz avec détermination de la pression différentielle |
DE102020206447A1 (de) * | 2020-05-25 | 2021-11-25 | Siemens Aktiengesellschaft | Verfahren zur Steuerung einer Elektrolysevorrichtung |
WO2022022849A1 (fr) * | 2020-07-30 | 2022-02-03 | Linde Gmbh | Maintien de pression dans un système d'électrolyse |
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2022
- 2022-05-09 EP EP22172254.9A patent/EP4276223A1/fr active Pending
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2023
- 2023-04-25 WO PCT/US2023/066147 patent/WO2023220520A1/fr unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190233957A1 (en) * | 2016-06-30 | 2019-08-01 | Siemens Aktiengesellschaft | Arrangement for the Electrolysis of Carbon Dioxide |
WO2021023435A1 (fr) * | 2019-08-08 | 2021-02-11 | Siemens Aktiengesellschaft | Procédé de conversion électrochimique d'un gaz de départ au niveau d'une électrode de diffusion de gaz avec détermination de la pression différentielle |
DE102020206447A1 (de) * | 2020-05-25 | 2021-11-25 | Siemens Aktiengesellschaft | Verfahren zur Steuerung einer Elektrolysevorrichtung |
WO2022022849A1 (fr) * | 2020-07-30 | 2022-02-03 | Linde Gmbh | Maintien de pression dans un système d'électrolyse |
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EP4276223A1 (fr) | 2023-11-15 |
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