CN115341228A - Device for preparing carbon monoxide by electrocatalysis - Google Patents
Device for preparing carbon monoxide by electrocatalysis Download PDFInfo
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- CN115341228A CN115341228A CN202210972269.0A CN202210972269A CN115341228A CN 115341228 A CN115341228 A CN 115341228A CN 202210972269 A CN202210972269 A CN 202210972269A CN 115341228 A CN115341228 A CN 115341228A
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000009792 diffusion process Methods 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 34
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 32
- 238000010521 absorption reaction Methods 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 75
- 238000007789 sealing Methods 0.000 claims description 42
- 239000004033 plastic Substances 0.000 claims description 35
- 229920003023 plastic Polymers 0.000 claims description 35
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims description 8
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- 239000007864 aqueous solution Substances 0.000 claims description 7
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- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000712 assembly Effects 0.000 claims 1
- 238000000429 assembly Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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
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- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a device for preparing carbon monoxide by electrocatalysis, comprising: the electrolytic cell comprises an electrolytic cell (1), an electrolyte circulating system, a gas supply device and a gas absorption device (7), wherein the electrolytic cell (1) is respectively connected with the electrolyte circulating system, the gas supply device and the gas absorption device; the gas absorption device (7) is provided with a carbon monoxide outlet (8). The device adopts a zero-polar distance design mode to attach and tightly press the cathode titanium mesh, the gas diffusion electrode, the proton exchange membrane and the anode mesh, so that the cell voltage is reduced to the maximum extent; the device uses pure water as the cathode electrolyte, so that the purity of the carbon monoxide product is improved; the gas diffusion electrode with uniform micropores promotes the gas-liquid mixing of carbon dioxide and water, improves the gas-liquid-solid three-phase interface, and increases the reaction area and the diffusion speed.
Description
Technical Field
The invention relates to a device for preparing carbon monoxide by electrocatalysis, belonging to the technical field of resource utilization of carbon dioxide.
Background
Global warming is a consequence of earth climate change caused by human behavior. "carbon" is a natural resource composed of carbon elements such as petroleum, coal, wood, etc. The "carbon" is much more consumed and the highly aggressive carbon dioxide that causes global warming is also much more produced. With the activities of human beings, global warming also affects the life style of people, and brings more and more problems.
In nature, carbon dioxide is converted into carbohydrates through photosynthesis, and this complicated process is difficult to reproduce industrially through human technological innovation. One currently technically feasible way is to electrochemically reduce carbon dioxide to higher energy products such as carbon monoxide, methane, alcohols, etc. And the electric energy can come from renewable energy sources such as wind power, photovoltaic, water power and the like. The emerging, clean and environment-friendly energy conversion mode has great significance for relieving greenhouse effect and realizing carbon neutralization.
At present, in an electrocatalysis carbon monoxide preparation device, in order to solve the problems of low solubility of carbon dioxide in an aqueous solution and low electrical conductivity of the aqueous solution, an organic solvent in which ionic liquid is dissolved or an aqueous solution in which inorganic supporting electrolyte is added is mostly adopted as catholyte. However, both of these methods result in the mixing of organic volatiles, inorganic impurities, etc. in the cathode reaction product, resulting in a decrease in the purity of carbon monoxide.
For the electrocatalytic reduction of carbon dioxide, metals are generally used as catalysts, and the method has the advantages of good conductivity and simple preparation. Different metal catalysts are selected, and the reduction products generated by electrocatalysis of carbon dioxide are different. Aiming at the technical characteristics, the invention selects a metal catalyst with high selectivity for generating carbon monoxide, such as gold, silver, zinc, scars and the like.
Disclosure of Invention
The invention aims to provide a device for preparing carbon monoxide by electrocatalysis.
The invention provides a device for preparing carbon monoxide by electrocatalysis, comprising: the electrolytic cell comprises an electrolytic cell (1), an electrolyte circulating system, a gas supply device and a gas absorption device (7), wherein the electrolytic cell (1) is respectively connected with the electrolyte circulating system, the gas supply device and the gas absorption device; the gas absorption device (7) is provided with a carbon monoxide outlet (8).
The electrolytic cell (1) comprises an anode chamber, a proton exchange membrane (16), a cathode chamber and a sealing and locking assembly;
the anode chamber consists of an anode end plate (9), an anode net, an anode plastic plate frame and a first sealing gasket (25):
in the invention, the anode plastic plate frame is an external wrapping structure of an anode end plate (9), the anode end plate is made of corrosion-resistant plastic, the anode end plate can be made of corrosion-resistant plastic such as PP, UPVC, PMMA and the like optionally, and flange holes are formed in four sides of the anode plastic plate frame and used for locking an electrolytic cell by bolts; an anode conductive column outlet (11) is arranged in the center of the anode end plate and used for extending out of the anode conductive column (13); an anolyte inlet (10) is arranged at the lower part of the back surface of the anode end plate, and a gas-liquid outlet (12) is arranged at the upper part of the back surface and used for discharging anolyte and oxygen generated by reaction; wherein the anolyte is an aqueous solution of an aqueous inorganic electrolyte.
The anode is an anode titanium mesh (15) coated with an oxide catalyst layer; the oxide catalyst layer can be one or more mixed noble metal oxides of ruthenium, iridium, rhodium, tantalum and titanium; meanwhile, the oxide catalyst layer can also be selected from rare earth oxides of one or a mixture of more of lanthanide rare earth elements such as cerium, neodymium and the like, and can also be noble metal oxides doped with rare earth elements; the anode conductive column (13) is vertically welded on the anode titanium mesh (15) in the middle; the other end of the anode conductive column (13) is designed with a section of screw teeth, and a round titanium sheet is welded below the screw teeth to be used as a first sealing platform (14). The sealing platform mainly serves for sealing the conductive columns.
The material of the anode plastic plate frame is the same as that of the anode end plate, the anode plastic plate frame is designed into a square flange form, an anode cavity is formed in the inner rectangular cavity, the outer size of the sealing gasket is the same as that of the plastic plate frame, the thickness of the sealing gasket is 0.5-3mm, and the material can be any one of polytetrafluoroethylene, fluororubber and ethylene propylene diene monomer rubber.
The cathode chamber consists of a cathode end plate (19), a cathode mesh (18), a gas diffusion electrode (17), a cathode plastic plate frame and a second sealing gasket (26); the cathode plastic plate frame is an external wrapping structure of a cathode end plate (19).
The design of the cathode end plate is similar to that of the anode end plate, and the difference is that the inlet position of the cathode end plate is close to the lower part and is flush with the flange hole at the lower end; the inlet is used for introducing carbon dioxide gas into the electrolytic cell; the design of the cathode net and the cathode conductive column is similar to that of the anode, and the difference is that the cathode net is made of one of pure titanium net, stainless steel net and nickel net; the cathode titanium mesh is used for compacting the gas diffusion electrode and transmitting electrons to the gas diffusion electrode; the lower part of the back surface of the cathode end plate is provided with a cathode end plate inlet (20), the upper part of the back surface is provided with a cathode end plate outlet (21),
the cathode end plate is centrally provided with a cathode conductive column outlet (22) for extending the cathode conductive column (23). The other end of the cathode conductive column (23) is also designed with a section of screw teeth, and a round titanium sheet is welded below the screw teeth to be used as a second sealing platform (24).
The sealing and locking assembly comprises an anode plastic plate frame, a first sealing gasket (25), a cathode plastic plate frame, a second sealing gasket (26) and bolts.
The design of the cathode plastic plate frame is similar to that of the anode plastic plate frame, and the difference is that a rectangular groove is sunk at the flange edge of the lower end of the cathode plastic plate frame; the inner side of the lower end of the cathode plastic plate frame is provided with a row of small holes communicated with the rectangular groove, and the carbon dioxide is transmitted to the rectangular groove of the cathode plastic plate frame from the inlet of the cathode end plate and then diffused to the gas diffusion electrode (17) through the row of small holes.
The electrolytic cell is assembled by sequentially passing a group of stainless steel bolts through an anode end plate, a sealing gasket, an anode plastic plate frame, a sealing gasket, a perfluorinated sulfonic acid proton exchange membrane, a sealing gasket, a cathode plastic plate frame, a sealing gasket and a cathode end plate and then locking and assembling, wherein the sealing gasket of a cathode chamber is provided with a rectangular hole corresponding to the rectangular groove of the cathode plastic plate frame and used for allowing carbon dioxide to pass through.
Further, the anode titanium mesh (15) in the anode chamber is a titanium-based DSA (dimensionally stable anode) electrode,
the cathode indoor cathode net (18) and the cathode conducting column (23) are similar to the design of the anode, and the difference is that the cathode net is made of one of a pure titanium net, a stainless steel net and a nickel net; the cathode mesh (18) is used for compacting the gas diffusion electrode and transmitting electrons to the gas diffusion electrode;
the cathode mesh (18) in the cathode chamber is designed as a gas or liquid diffusion electrode; the surface of the gas diffusion electrode (17) contains a catalyst layer; the electrolyte in the cathode chamber is an aqueous electrolyte, and the electrolyte is permeated and supplemented through a proton exchange membrane (16);
the electrolyte circulating system comprises a liquid storage tank (2), a circulating pump (3) and a gas-liquid separator (4), wherein the liquid storage tank (2) is respectively connected with the circulating pump (3) and the gas-liquid separator (4); the circulating pump (3) and the gas-liquid separator (4) are respectively connected with an anolyte inlet (10) and a gas-liquid outlet (12) and are used for circulating the anolyte, wherein the anolyte is an aqueous solution added with inorganic electrolyte, such as dilute sulfuric acid with the concentration of 0.1-1mol/L and sodium sulfate aqueous solution optionally. The gas-liquid separator (4) is provided with an oxygen outlet (5).
The gas supply device is connected with the inlet (20) of the cathode end plate, and the gas supply device is a carbon dioxide compressor (6) and is used for supplying carbon dioxide gas into the cathode chamber.
Further, the gas supply device is a compressor or a conveying device suitable for carbon dioxide gas and a pipeline, a valve and a pressure gauge matched with the compressor or the conveying device, and the pressure output of the carbon dioxide gas is 0.1-0.4MPa.
The gas absorption device (7) is connected to the cathode end plate outlet (21) and is used for absorbing unreacted carbon dioxide gas.
Furthermore, the gas absorption device (7) is a counter-flow gas absorption tower, and the absorption liquid is sprayed downwards to absorb the unreacted carbon dioxide in the mixed gas and improve the purity of the carbon monoxide gas. The gas absorption device (7) is connected to the outlet of the cathode chamber and is used for absorbing and separating unreacted carbon dioxide gas; the unreacted carbon dioxide gas is recycled before returning to the air inlet device.
Furthermore, as another embodiment, the gas absorption device (7) can also adopt a membrane separation device.
Furthermore, the proton exchange membrane (16) is closely attached to the gas diffusion electrode (17), protons permeate the proton exchange membrane (16) to react with carbon dioxide on the surface of the gas diffusion electrode (17), and generated carbon monoxide reaches the outlet (21) of the electrolytic cell through the pores of the gas diffusion electrode (17) and enters the gas absorption device (7).
In the invention, a proton exchange membrane (16), an anode net (15), a cathode net (18) and a gas diffusion electrode (17) are closely attached together to meet the design requirement of zero polar distance; and effectively support the proton exchange membrane, and prevent the deformation and damage of the proton membrane caused by the gas-liquid pressure difference of the cathode chamber and the anode chamber. During electrocatalytic reaction, protons permeate through the proton exchange membrane (16) to react with carbon dioxide on the surface of the gas diffusion electrode (17), and the generated carbon monoxide reaches the outlet of the electrolytic cell through the pores of the gas diffusion electrode (17) and enters the gas absorption and separation device; electrolyte in the cathode chamber is supplemented by water molecules penetrating through the proton exchange membrane (16), and a cathode electrolyte circulating feeding device is not required to be configured.
Further, the proton exchange membrane (16) of the present invention is a perfluorosulfonic acid proton exchange membrane.
Furthermore, the gas diffusion electrode (17) is a foamed titanium plate, a foamed nickel plate or a stainless steel plate with uniform micropores, and one or more of gold, silver, zinc and palladium or gold, silver, zinc and palladium doped with trace rare earth elements are loaded on the surface of the gas diffusion electrode to serve as a catalyst;
preferably, the catalyst zinc loaded on the surface of the gas diffusion electrode (17) refers to layered porous zinc oxide nano-particles synthesized by annealing basic zinc carbonate precursor; the trace rare earth element is one or more of rare earth lanthanide elements. The gas diffusion electrode (17) is the main place where carbon dioxide enters the cathode chamber, diffuses and breaks into micro bubbles or liquid drops, and obtains electrons to be reduced into carbon monoxide.
The invention has the beneficial effects that:
in order to make up the defects of the prior art, the device adopts a design mode of zero polar distance to attach and compress the cathode titanium mesh, the gas diffusion electrode, the proton exchange membrane and the anode mesh, so that the cell voltage is reduced to the maximum extent; the device uses pure water as the cathode electrolyte, so that the purity of the carbon monoxide product is improved; the gas diffusion electrode with uniform micropores promotes the gas-liquid mixing of carbon dioxide and water, improves the gas-liquid-solid three-phase interface, and increases the reaction area and the diffusion speed.
Drawings
FIG. 1 is a schematic diagram of the structure of an electrocatalytic carbon monoxide production plant.
FIG. 2 is a schematic view of the structure of the electrolytic cell.
FIG. 3 is a schematic structural diagram of the positions of the first sealing gasket and the second sealing gasket in the electrolytic cell.
In the figure: in the figure: 1-an electrolytic tank, 2-a liquid storage tank, 3-a circulating pump, 4-a gas-liquid separator, 5-an oxygen outlet, 6-a carbon dioxide compressor, 7-a gas absorption tower, 8-a carbon monoxide outlet,
9-anode end plate, 10-anode end plate inlet, 11-anode conductive column outlet, 12-anode end plate outlet, 13-anode conductive column, 14-first sealing platform, 15-anode titanium net, 16-proton exchange membrane, 17-gas diffusion electrode, 18-cathode net, 19-cathode end plate, 20-cathode end plate inlet, 21-cathode end plate outlet, 22-cathode conductive column outlet, 23-cathode conductive column, and 24-second sealing platform. 25-the first gasket, 26-the second gasket.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
fig. 1 discloses a structure of an electrocatalytic carbon monoxide production apparatus, comprising:
an electrolytic cell having an anode compartment, a proton exchange membrane 16, a cathode compartment, a seal and lock assembly; wherein the anode in the anode chamber is a long-life IrO 2. Ta2O5 mixed oxide titanium mesh 15 doped with rare earth elements; the proton exchange membrane 16 uses a dupont N117 type perfluorosulfonic acid proton membrane; the cathode in the cathode chamber is designed as a gas diffusion electrode 17 whose surface contains a catalyst layer; the electrolyte in the cathode chamber is pure water, and the water permeated through the proton exchange membrane is supplemented;
in the anode chamber, the electrolyte generates oxygen evolution reaction on the anode net interface under the action of a catalyst as follows:
in the cathode chamber, CO is contained 2 The electrolyte reacts on the diffusion electrode interface under the action of the catalyst as follows:
an electrolyte circulating system, which consists of a liquid storage tank 2, a circulating pump 3, a gas-liquid separator 5, a pipeline and a valve; the circulating pump 3 pumps the anolyte from the liquid storage tank 2 to be injected into the anode chamber through an anode end plate inlet 10 at the lower end of the anode end plate, and after oxygen and anolyte mixture generated by reaction enter a gas-liquid separator 5 from an anode end plate outlet 12 at the upper end of the anode end plate, the oxygen is discharged to the atmosphere through a pipeline of the oxygen outlet 5, and the anolyte flows back to the liquid storage tank; anolyte is 0.5mol/L dilute sulphuric acid;
an air inlet device, which uses a carbon dioxide compressor 6 to pump carbon dioxide gas into the cathode chamber through a cathode end plate inlet 20 at the lower end of the cathode end plate, and carbon monoxide and carbon dioxide mixed gas carrying part water generated by reaction is discharged from a cathode end plate outlet 21 at the upper end of the cathode end plate; the carbon dioxide inlet pressure is controlled to be 0.1MPa;
a counter-current gas absorption column; and a cathode end plate outlet 21 connected to the cathode chamber, wherein the absorption liquid is sprayed downwards to absorb unreacted carbon dioxide in the mixed gas, so that the purity of the carbon monoxide gas is improved.
As shown in fig. 2, a proton exchange membrane 16 in the electrolytic cell is closely attached to an anode titanium mesh 15, a gas diffusion electrode 17 and a cathode mesh 18, so as to meet the design requirement of zero polar distance; and effectively supports the proton exchange membrane, and prevents the deformation and damage of the proton membrane caused by the gas-liquid pressure difference between the cathode chamber and the anode chamber. Electrolyte in the cathode chamber is supplemented by water molecules penetrating through the proton exchange membrane, and a cathode electrolyte circulating feeding device is not required to be configured.
The electrolytic cell consists of an anode end plate 9, an anode titanium mesh 15, an anode plastic plate frame, a sealing gasket, a proton exchange membrane 16, a sealing gasket, a cathode plastic plate frame, a cathode mesh 18, a gas diffusion electrode 17, a cathode end plate 19 and bolts. Wherein the anode end plate and the cathode end plate are processed by UPVC plates with the thickness of 20 mm; the anode titanium net 15 and the cathode net 18 are made of pure titanium, the thickness of the anode titanium net is 2mm, the mesh is 12 x 6 x 1.5mm, and the middle part of the anode titanium net and the cathode net is vertically welded with a conductive column with a sealing platform; the anode plastic plate frame and the cathode plastic plate frame are processed by UPVC plates with the thickness of 5 mm; the sealing gasket is 2mm and is made of fluororubber; the gas diffusion electrode used 2 layers of thickness 2mm foam titanium plate, the surface gold plating as active catalyst.
The assembly steps of the electrolytic cell are as follows:
firstly, installing a fluorine rubber O-shaped ring on a first sealing platform 14 of an anode conductive column 13, then extending out from a central hole of an anode end plate 9 and locking a nut, so that the anode end plate and an anode net form an integral assembly;
secondly, assembling the cathode mesh 18 and the cathode end plate 19 together in the same manner to form an integral assembly;
thirdly, a group of stainless steel bolts penetrate through the anode end plate assembly, the bolts are flatly placed on the table top upwards, and then the sealing gasket, the anode plastic plate frame, the sealing gasket, the perfluorinated sulfonic acid proton exchange membrane 16, the sealing gasket, the cathode plastic plate frame, the gas diffusion electrode 17, the sealing gasket and the cathode end plate assembly penetrate through the bolts and the locking nuts in sequence; during the assembly process, the corresponding positions of the inlets and the outlets and the rectangular grooves of the cathode plastic plate frame are particularly noticed;
and fourthly, mounting standard pipe fittings of each inlet and outlet on the anode end plate and the cathode end plate.
Particularly, the force and the stroke need to be controlled when the stainless steel nut is locked, so that the distances between the anode end plate and the cathode end plate in all directions are basically equal; and the compression amount of the sealing gasket is controlled, so that the anode net, the perfluorinated sulfonic acid proton exchange membrane, the gas diffusion electrode and the cathode net in the electrolytic cell are bonded and pressed without pressure deformation.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof.
Claims (10)
1. An electrocatalytic carbon monoxide production plant, comprising: the electrolytic cell (1) is respectively connected with the electrolyte circulating system, the gas supply device and the gas absorption device (7); the gas absorption device (7) is provided with a carbon monoxide outlet (8).
2. The electrocatalytic carbon monoxide production plant as set forth in claim 1, wherein the electrolyzer (1) comprises an anode compartment, a proton exchange membrane (16), a cathode compartment, sealing and locking assemblies;
the anode chamber consists of an anode end plate (9), an anode net, an anode plastic plate frame and a first sealing gasket (25):
the anode end plate is made of corrosion-resistant plastic, and flange holes are formed in the four sides of the anode end plate and used for locking the electrolytic cell through bolts; an anode conductive column outlet (11) is arranged in the center of the anode end plate and used for extending out of the anode conductive column (13); an anolyte inlet (10) is arranged at the lower part of the back surface of the anode end plate, and a gas-liquid outlet (12) is arranged at the upper part of the back surface and used for discharging anolyte and oxygen generated by reaction; wherein the anolyte is an aqueous solution of an aqueous inorganic electrolyte;
the anode is an anode titanium mesh (15) coated with an oxide catalyst layer; the oxide catalyst layer can be one or more mixed noble metal oxides of ruthenium, iridium, rhodium, tantalum and titanium; the anode conductive column (13) is vertically welded on the anode titanium mesh (15) in the middle; a section of screw thread is designed at the other end of the anode conductive column (13), and a round titanium sheet is welded below the screw thread to be used as a first sealing platform (14);
the material of the anode plastic plate frame is the same as that of the anode end plate, and the anode plastic plate frame is designed into a square flange form; the outer dimension of the sealing gasket is the same as that of the plastic plate frame, the thickness of the sealing gasket is 0.5-3mm, and the material of the sealing gasket can be any one of polytetrafluoroethylene, fluororubber and ethylene propylene diene monomer rubber;
the cathode chamber consists of a cathode end plate (19), a cathode mesh (18), a gas diffusion electrode (17), a cathode plastic plate frame and a second sealing gasket (26);
the lower part of the back of the pole end plate is provided with a cathode end plate inlet (20), the upper part of the back is provided with a cathode end plate outlet (21),
a cathode conductive column outlet (22) is arranged in the center of the cathode end plate and used for extending out of the cathode conductive column (23); a section of screw thread is also designed at the other end of the cathode conductive column (23), and a round titanium sheet is welded below the screw thread to be used as a second sealing platform (24);
the sealing and locking assembly comprises an anode plastic plate frame, a first sealing gasket (25), a cathode plastic plate frame, a second sealing gasket (26) and bolts.
3. The device for preparing carbon monoxide by electrocatalysis according to claim 2, wherein the anode titanium mesh (15) in the anode chamber is a titanium-based DSA (dimensionally stable anode) electrode.
4. The device for preparing carbon monoxide by electrocatalysis according to claim 2, wherein the cathode mesh (18) in the cathode chamber is made of one of pure titanium mesh, stainless steel mesh and nickel mesh.
5. The electrocatalysis carbon monoxide preparation device according to claim 1, wherein the electrolyte circulating system comprises a liquid storage tank (2), a circulating pump (3) and a gas-liquid separator (4), the liquid storage tank (2) is respectively connected with the circulating pump (3) and the gas-liquid separator (4), and the circulating pump (3) and the gas-liquid separator (4) are respectively connected with the anode liquid inlet (10) and the gas-liquid outlet (12); the gas-liquid separator (4) is provided with an oxygen outlet (5).
6. The device for producing carbon monoxide by electrocatalysis as claimed in claim 1, wherein said gas supply means is connected to the cathode end plate inlet (20), said gas supply means being a carbon dioxide compressor (6) for supplying carbon dioxide gas into the cathode chamber.
7. The electrocatalytic carbon monoxide production plant as set forth in claim 1, wherein said gas absorption means is connected to the cathode end plate outlet (21) for absorbing unreacted carbon dioxide gas.
8. The electrocatalytic carbon monoxide production apparatus as set forth in claim 7, wherein said gas absorption unit (7) is a counter-current gas absorption tower, and the absorption liquid is sprayed downward to absorb the unreacted carbon dioxide in the mixed gas, thereby increasing the purity of the carbon monoxide gas.
9. The electrocatalytic carbon monoxide production plant as set forth in claim 7, wherein said gas absorption unit (7) can also be a membrane separation unit.
10. The electrocatalytic carbon monoxide production plant as set forth in claim 2, wherein said proton exchange membrane (16) is closely attached to said gas diffusion electrode (17), and protons react with carbon dioxide on the surface of the gas diffusion electrode (17) through the proton exchange membrane (16), and the produced carbon monoxide enters the gas absorption device (7) through the pores of the gas diffusion electrode (17) to the outlet (21) of the electrolytic cell; electrolyte in the cathode chamber is supplemented by protons permeating through the proton exchange membrane, and a cathode electrolyte circulating feeding device is not required to be configured.
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