CN115094454B - Electrolytic cell and method for urea electrolysis hydrogen production and carbon reduction - Google Patents
Electrolytic cell and method for urea electrolysis hydrogen production and carbon reduction Download PDFInfo
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an electrolytic cell and a method for producing hydrogen and reducing carbon by urea electrolysis, wherein the electrolytic cell comprises a shell, a cathode chamber, an anode chamber and a chemical conversion chamber; the shell is internally provided with a cathode, a diaphragm and an anode in sequence, and a space is reserved between adjacent two of the cathode, the diaphragm and the anode; the anode is a gas diffusion electrode; the cathode chamber is a closed chamber formed by sealing a cathode, a diaphragm and the inner wall of the shell; an alkaline aqueous solution is arranged in the cathode chamber; the anode chamber is a closed chamber formed by sealing the diaphragm, the anode and the inner wall of the shell; an alkaline urea solution is arranged in the anode chamber; the chemical conversion chamber is a closed chamber formed by sealing the anode and the inner wall of the shell; a carbon dioxide absorbent is arranged in the chemical conversion chamber. The electrolytic cell for producing hydrogen and reducing carbon by urea electrolysis can improve the reaction efficiency of producing hydrogen by electrolysis, reduce the overall cost of the process, avoid the release of carbon dioxide and achieve the aim of zero carbon emission.
Description
Technical Field
The invention belongs to the technical field of electrolytic hydrogen production and carbon dioxide utilization, and particularly relates to an electrolytic cell and a method for urea electrolytic hydrogen production and carbon reduction.
Background
At present, the hydrogen production by water electrolysis is the only technical way capable of realizing industrial green hydrogen production. In order to improve the cost competitiveness of green hydrogen produced by water electrolysis hydrogen production, the electricity consumption of water electrolysis hydrogen production needs to be further reduced. The urea is used as an electrolyte additive, so that theoretical energy consumption of electrolytic hydrogen production can be reduced in principle (only 1/5 of that of direct electrolytic water), and the urea can be obtained from industrial waste or human and animal urine, has the additional effect of purifying waste water while obtaining hydrogen, and is a good hydrogen production cost-reducing way.
However, the electrolytic hydrogen production system that adds urea as an electrolyte has the following problems: carbon dioxide generated by the anode is easy to be converted into carbonate in an alkaline environment, carbonic acid crystals are easy to be formed, membrane blockage is caused, performance of electrolytic hydrogen production is affected, voltage is increased, service life is shortened and the like; the consumption of alkaline ions by carbon dioxide also causes additional costs. In addition, even if carbon dioxide is not converted to carbonate, its emissions can cause pollution; the cross-membrane mixing of carbon dioxide and hydrogen can result in reduced hydrogen quality, leading to increased cost for subsequent purification. Therefore, the problems of carbon dioxide generated in the urea electrolysis hydrogen production process need to be solved, and the direct emission of carbon dioxide and the pollution to hydrogen, the consumption of alkaline ions by carbon dioxide and the pollution and blockage of carbonate are avoided.
Disclosure of Invention
Therefore, one object of the present invention is to provide an electrolytic cell for producing hydrogen and reducing carbon by electrolysis of urea, wherein a gas diffusion electrode with high conductivity and porosity is adopted as an anode, so that carbon dioxide generated by electrolysis of urea can be separated from an anode chamber in time in the reaction process and enter a chemical conversion chamber to be reduced, consumption of hydroxyl ions in an alkaline system by carbon dioxide can be avoided, pollution and blockage of an electrolytic membrane can be reduced, the reaction efficiency of hydrogen production by electrolysis can be improved, and the overall cost of the process can be reduced; meanwhile, the mixing pollution of carbon dioxide to the product hydrogen can be reduced, the release of carbon dioxide is avoided, and the purpose of zero carbon emission is achieved.
Another object of the invention is to propose a process for the electrolytic hydrogen production and carbon reduction of urea.
To achieve the above object, an embodiment of a first aspect of the present invention provides an electrolytic cell for producing hydrogen and reducing carbon by electrolysis of urea, comprising a housing, a cathode chamber, an anode chamber, and a chemical conversion chamber;
the shell is internally provided with a cathode, a diaphragm and an anode in sequence, and the cathode, the diaphragm and the anode are arranged in parallel; the anode is a gas diffusion electrode; the anode is connected with the positive electrode of the external power supply, and the cathode is connected with the negative electrode of the external power supply;
the cathode chamber is a closed chamber formed by sealing a cathode, a diaphragm and the inner wall of the shell; an alkaline aqueous solution is arranged in the cathode chamber;
the anode chamber is a closed chamber formed by sealing the diaphragm, the anode and the inner wall of the shell; an alkaline urea solution is arranged in the anode chamber;
the chemical conversion chamber is a closed chamber formed by sealing an anode and the inner wall of the shell; a carbon dioxide absorbent is arranged in the chemical conversion chamber; or a solvent and a chemical catalyst are arranged in the chemical conversion chamber; or a solvent and a photocatalyst are arranged in the chemical conversion chamber.
According to the electrolytic cell for hydrogen production and carbon reduction by urea electrolysis, the anode adopts the gas diffusion electrode with high conductivity and porosity, so that carbon dioxide generated by urea electrolysis can be separated from the anode chamber in time in the reaction process and enter the chemical conversion chamber to be reduced, the consumption of the carbon dioxide on hydroxyl ions in an alkaline system can be avoided, the pollution and blockage of an electrolytic diaphragm can be reduced, and the reaction efficiency of hydrogen production by electrolysis can be improved; meanwhile, the mixing pollution of carbon dioxide to the product hydrogen can be reduced, the release of carbon dioxide is avoided, and the purpose of zero carbon emission is achieved.
In addition, the electrolytic cell for producing hydrogen and reducing carbon by urea electrolysis according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, the cathode is a conductive substrate provided with a load layer on the surface; the conductive substrate is a metal plate or a porous plate; the material of the load layer is one or more than two of Pt, ru, rh, ir, ni, co, fe, zn, ti.
In some embodiments of the invention, the membrane is a porous membrane or has OH - A conductive anion exchange membrane; the porous diaphragm is a Zirfon film; the anion exchange membrane is a polyarylether membrane, a polyethylene membrane, a polystyrene membrane, a polytetrafluoroethylene membrane or a polyphenyl membrane modified with cationic groups; the cationic group is a polyalkylammonium salt, an imidazole salt, a pyridine salt or a piperidine salt.
In some embodiments of the invention, the anode is a porous substrate with an active catalytic layer supported on the surface; the porous matrix is foam metal or carbon material; the material of the active catalytic layer is one or more than two of Pt, ru, rh, ir, ni, co, fe, zn, ti.
In some embodiments of the invention, the carbon dioxide absorbent fills the chemical conversion chamber; the carbon dioxide absorbent is an amine organic absorbent.
In some embodiments of the invention, the solvent and chemical catalyst fill the chemical conversion chamber; the solvent is an alcohol organic solvent, an amine organic solvent or water; the chemical catalyst is composite metal particles supported by an organic porous carrier or composite metal particles supported by an inorganic porous carrier.
In some embodiments of the invention, the solvent and photocatalyst fill the chemical conversion chamber; the photocatalyst is a semiconductor material supported cocatalyst; the shell is made of light-transmitting materials.
In some embodiments of the invention, the solvent is an alcoholic organic solvent, an amine organic solvent, or water; the photocatalyst is a cuprous oxide nanocrystalline catalyst loaded by graphite-phase carbon nitride.
In some embodiments of the present invention, a circulation pump is installed on both the liquid inlet communication line and the liquid outlet communication line of the chemical conversion chamber, for driving the carbon dioxide absorbent or the solvent in the chemical conversion chamber to circulate.
To achieve the above object, an embodiment of a second aspect of the present invention provides a method for producing hydrogen and reducing carbon by electrolysis of urea, comprising:
electrolyzing water in the cathode chamber to generate hydrogen;
electrolyzing the alkaline urea solution in an anode chamber to convert urea into nitrogen, carbon dioxide and water;
carbon dioxide in the anode chamber enters a chemical conversion chamber through the anode, and is converted into carbon monoxide, formic acid, formaldehyde, methanol or C in the chemical conversion chamber through chemical absorption, chemical catalytic reduction or photo catalytic reduction 2+ And (3) hydrocarbon fuel.
The method for producing hydrogen and reducing carbon by urea electrolysis in the embodiment of the invention has the same advantages as the electrolytic cell for producing hydrogen and reducing carbon by urea electrolysis in the embodiment of the invention, and is not repeated here.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic view of a simple structure of an electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to one embodiment of the invention.
Fig. 2 is a schematic view of a simple structure when a carbon dioxide absorbent is provided in an anode chamber of an electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to an embodiment of the present invention.
Fig. 3 is a schematic view of a simple structure when an anode chamber of an electrolytic cell for urea electrolysis hydrogen production and carbon reduction is provided with a chemical catalyst according to an embodiment of the present invention.
Reference numerals:
1-a cathode; 2-a separator; 3-anode; 4-a housing; 5-an external power source; 6-a chemical catalyst; 10-cathode chamber; 20-anode chamber; 30-chemical conversion chamber.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The chemical reagents and equipment involved in the embodiment of the invention are conventional commercial chemical reagents and equipment unless specified otherwise; the methods according to the embodiments of the present invention are conventional methods unless otherwise specified.
An electrolytic cell for urea electrolysis hydrogen production and carbon reduction, a method for urea electrolysis hydrogen production and carbon reduction according to an embodiment of the present invention are described below with reference to the accompanying drawings.
FIG. 1 is a schematic view of a simple structure of an electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to one embodiment of the invention.
As shown in fig. 1, an electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to an embodiment of the present invention includes a housing 4, a cathode chamber 10, an anode chamber 20, and a chemical conversion chamber 30; the cathode 1, the diaphragm 2 and the anode 3 are sequentially arranged in the shell 4, and the cathode 1, the diaphragm 2 and the anode 3 are arranged in parallel; the anode 3 is a gas diffusion electrode; the anode 3 is connected with the positive electrode of the external power supply 5, and the cathode 1 is connected with the negative electrode of the external power supply 5; the cathode chamber 10 is a closed chamber formed by sealing the cathode 1, the diaphragm 2 and the inner wall of the shell 4; an alkaline aqueous solution is arranged in the cathode chamber 10; the anode chamber 20 is a closed chamber formed by sealing the inner walls of the diaphragm 2, the anode 3 and the shell 4; an alkaline urea solution is arranged in the anode chamber 20; the chemical conversion chamber 30 is a closed chamber formed by sealing the anode 3 and the inner wall of the shell 4; a carbon dioxide absorbent is arranged in the chemical conversion chamber 30; alternatively, the chemical conversion chamber 30 is provided with a solvent and a chemical catalyst 6; alternatively, the chemical conversion chamber 30 is provided with a solvent and a photocatalyst.
According to the electrolytic cell for hydrogen production and carbon reduction by urea electrolysis, the anode adopts the gas diffusion electrode with high conductivity and porosity, so that carbon dioxide generated by urea electrolysis can be separated from the anode chamber in time in the reaction process and enter the chemical conversion chamber to be reduced, the consumption of hydroxyl ions in an alkaline system by the carbon dioxide can be avoided, the pollution and blockage of an electrolytic diaphragm can be reduced, the reaction efficiency of hydrogen production by electrolysis can be improved, and the overall cost of the process can be reduced; meanwhile, the mixing pollution of carbon dioxide to the product hydrogen can be reduced, the release of carbon dioxide is avoided, and the purpose of zero carbon emission is achieved.
Alternatively, in some embodiments of the invention, the side of the cathode 1 remote from the membrane 2 may be in close proximity to the inner wall of the housing 4 immediately adjacent thereto; in other embodiments of the invention, the side of the cathode 1 remote from the separator 2 may also be spaced from the housing 4 immediately adjacent thereto (as shown in fig. 1).
Alternatively, the cathode 1, the diaphragm 2 and the anode 3 may be welded to the inner wall of the casing 4 or be connected with the inner wall of the casing 4 by sealing rings, bolts, etc., so long as the cathode chamber 10, the anode chamber 20 and the chemical conversion chamber 30 are all sealed chambers.
The shape of the case is not limited, and may be rectangular parallelepiped, square, cylindrical, or the like. Alternatively, in some embodiments of the present invention, when the carbon dioxide absorbent is disposed in the chemical conversion chamber 30 or the solvent and the chemical catalyst 6 are disposed in the chemical conversion chamber 30, the material of the housing is not limited, and may be a metal material such as stainless steel or a corrosion-resistant plastic material such as polytetrafluoroethylene. In other embodiments of the present invention, when the solvent and the photocatalyst are provided in the chemical conversion chamber 30, the material of the housing is preferably a light-transmitting material such as polymethyl methacrylate (PMMA), polystyrene (PS), polycarbonate (PC), and polydiallyldiglycol carbonate (CR-39), because the photocatalyst needs to receive natural light or light emitted from an external light source.
Alternatively, in some embodiments of the present invention, the cathode 1, the separator 2, and the anode 3 may be disposed at different angles to each other, in addition to being disposed parallel to each other; so long as the cathode and separator and the housing can form a cathode chamber, the separator and anode and the housing can form an anode chamber, and the anode and the housing can form a chemical conversion chamber. Preferably, for convenient processing and installation, the shell is cuboid or square, and cathode 1, diaphragm 2, positive pole 3 three parallel arrangement, and all set up with shell top and bottom vertically.
Alternatively, in some embodiments of the invention, the aqueous alkaline solution is a 20-30wt% potassium hydroxide solution; the alkaline urea solution is a mixed solution of potassium hydroxide, urea and water, and the contents of the potassium hydroxide and the urea in the mixed solution are respectively 20-30wt% and 1-10wt%. Preferably, the aqueous alkaline solution is a 25wt% potassium hydroxide solution; the alkaline urea solution is a mixed solution of potassium hydroxide, urea and water, and the content of the potassium hydroxide and the urea in the mixed solution is 25wt% and 5wt% respectively
Alternatively, in some embodiments of the present invention, the cathode 1 is a conductive substrate provided with a load layer on the surface. Wherein in some embodiments the conductive substrate may be selected from a metal plate, such as a copper plate, a stainless steel plate, etc., in other embodiments the conductive substrate may be selected from a porous plate of foam metal, such as foam nickel, foam copper, foam iron-nickel alloy, foam nickel-molybdenum alloy, etc., or a carbon material, such as graphite, activated carbon, etc. Alternatively, the material of the supporting layer may be one or more than two of Pt, ru, rh, ir, ni, co, fe, zn, ti. Alternatively, in some embodiments of the invention, the conductive substrate has a thickness of 100-500 microns and the loading layer has a thickness of 5-100 nanometers.
It should be noted that, in some embodiments of the present invention, the preparation method of the conductive substrate provided with the load layer includes: the material of the supporting layer is formed on the conductive substrate by electrodeposition, dipping, etc., and the specific forming method, process conditions, etc. are conventional techniques in the art and are not the focus of the embodiments of the present invention.
Wherein, the electrochemical reaction of the surface of the cathode 1 is as follows:
6H 2 O+6e - →3H 2 +6OH - 。
alternatively, in some embodiments of the invention, the membrane 2 may be selected to be a porous membrane, such as a commercial Zirfon membrane (85 wt% ZrO loaded) 2 Nanoparticle polysulfone), and the like; in other embodiments of the invention, the membrane 2 may optionally have OH - Conductive anion exchange membranes. Preferably, the anion exchange membrane may be a polyarylether membrane, a polyethylene membrane, a polystyrene membrane, a polytetrafluoroethylene membrane or a polyphenyl membrane modified with cationic groups, wherein the cationic groups may be a polyalkylammonium salt, an imidazolium salt, a pyridinium salt or a piperidinium salt, for example, the polyalkylammonium salt may be a trialkyl quaternary ammonium salt, a trimethyl quaternary ammonium salt or the like.
In some embodiments of the invention, have OH - The preparation method of the anion exchange membrane with the conduction function comprises the following steps: polymerization of monomers (direct polymerization of monomers modified with cationic groups with structural groups, for example quaternary ammonium poly (N-methyl-piperidine-co-p-terphenyl) (QAPPT) -
1) The reaction of terphenyl with N-methyl-4-piperidone under the catalysis of trifluoromethanesulfonic acid and trifluoroacetic acid forms a linear polymer. 2) Conversion of the piperidine groups of the polymer to quaternary ammonium salts: in NMP/DMSO mixed solvent, at 70deg.C with CH 3 I reaction. 3) Final formation of QAPPT with OH-: treating with KOH solution for a period of time. ) Or post-modification (modification of the polymer film directly by cationic group modification). For example, a polytetrafluoroethylene film is used as a base material, chloromethylstyrene is modified thereon by a grafting reaction, and then a trimethylamine solution and a KOH solution are used for quaternary ammoniumChemical and alkalization reactions).
Alternatively, in some embodiments of the invention, the anode 3 is a porous substrate with an active catalytic layer supported on the surface. The porous matrix can be selected from foam metal or carbon material, the foam metal can be selected from foam nickel, foam copper, foam iron-nickel alloy, foam nickel-molybdenum alloy, etc., and the carbon material can be selected from graphite, activated carbon, etc. The material of the active catalytic layer is one or more than two of Pt, ru, rh, ir, ni, co, fe, zn, ti. Preferably, the thickness of the porous matrix is 100-500 microns, the average pore diameter is 10-20 microns, and the porosity is 20-60%; the thickness of the active catalytic layer is 5-100 nanometers. The anode adopts a gas diffusion electrode with high conductivity and porosity, so that carbon dioxide generated by urea electrolysis can be separated from an electrolysis anode chamber system in time in the reaction process, the consumption of hydroxyl ions in an alkaline system by the carbon dioxide is avoided, the pollution and blockage of an electrolysis diaphragm are reduced, and the reaction efficiency of electrolytic hydrogen production is improved.
In some embodiments of the present invention, the method for preparing the porous substrate with the active catalytic layer supported on the surface comprises: the material of the active catalytic layer is formed on the porous substrate by electrodeposition, impregnation or the like, and the specific forming method, process conditions and the like are conventional techniques in the art and are not important in the embodiment of the present invention.
Wherein the electrochemical reaction of the surface of the anode 3 is as follows:
CO(NH 2 ) 2 +6OH - →N 2 +5H 2 O+CO 2 +6e - 。
in embodiments of the present invention, carbon dioxide is absorbed or converted in the form of chemisorption, chemocatalytic reduction, photocatalytic reduction, etc., within the chemical conversion chamber.
Principle of chemical absorption: a chemical absorption liquid having an alkaline property is used to absorb carbon dioxide by chemically reacting with carbon dioxide. (unstable salts (such as bicarbonate) are generated in the absorption process, and then the unstable salts are sent into a regeneration tower, so that the unstable salts can be decomposed by heating, and carbon dioxide with higher concentration is obtained, and the absorbent is sent into the absorption tower for further absorption after regeneration.) commonly used absorbent at present comprises ammonia water solution, calcium-based absorption liquid, potassium carbonate solution, strong alkali solution, organic alcohol amine solution and the like.
Principle of catalytic reduction: under the action of chemical catalyst or photocatalyst, carbon dioxide is reduced to produce organic matter or intermediate product, such as CO, formic acid, formaldehyde, methanol or C 2+ Hydrocarbon fuels, and the like. The common photocatalytic carbon dioxide reduction products and the corresponding potentials are shown in table 1.
TABLE 1 photocatalytic carbon dioxide reduction products and corresponding potentials
| CO 2 Reduction reaction | E(V(vs.NHE)) |
| CO 2 +e - →CO 2 · - | -1.9 |
| CO 2 +2H + +2e - →CO+H 2 O | -0.53 |
| CO 2 +2H + +2e - →HCOOH | -0.61 |
| CO 2 +4H + +4e - →HCHO+H 2 O | -0.48 |
| CO 2 +6H + +6e - →CH 3 OH+H 2 O | -0.38 |
| CO 2 +8H + +8e - →CH 4 +H 2 O | -0.24 |
| 2H + +2e - →H 2 | -0.41 |
The chemical conversion chamber adopts a solvent which is favorable for dissolving or absorbing carbon dioxide, so that the carbon dioxide generated and diffused from the anode reaches the surface of the chemical catalyst in time, and meanwhile, a chemical conversion system (carbon dioxide absorbent, or solvent and chemical catalyst, or solvent and photocatalyst) is in a fluidized state, which is favorable for reducing the carbon dioxide to form a valuable product, promotes the balance of the electrolytic reaction to move forward, improves the overall reaction efficiency, reduces the mixing pollution of the carbon dioxide to the hydrogen of the product, avoids the release of the carbon dioxide, and achieves the purpose of zero carbon emission.
Alternatively, in some embodiments of the present invention, circulation pumps are installed on both the liquid inlet communication line and the liquid outlet communication line of the chemical conversion chamber 30 for driving the carbon dioxide absorbent or the solvent in the chemical conversion chamber 30 to circulate. The liquid inlet and the liquid outlet of the chemical absorption chamber can be respectively arranged at the top and the bottom of the shell corresponding to the chemical absorption chamber; in addition, the chemical absorption chamber can be provided with a gas outlet at the top of the corresponding shell for discharging nitrogen generated by urea electrolysis and entering the chemical absorption chamber.
Alternatively, in some embodiments of the invention, the carbon dioxide absorbent fills the chemical conversion chamber 30 (shown in FIG. 2) as the carbon dioxide is absorbed in a chemically absorbed form within the chemical conversion chamber. The interface between the carbon dioxide absorbent and the anode 3 is stable due to the phase separation, the carbon dioxide absorbent is in a continuous circulation state, the enriched carbon dioxide is transferred outside the chemical conversion chamber, and the carbon dioxide is further separated from the carbon dioxide absorbent (in the form of heating and the like) for food production or further conversion. The carbon dioxide absorbent is preferably an organic absorbent, more preferably an amine-based organic absorbent such as monoethanolamine, diethanolamine, N-ethylethanolamine, 2-amino-2-methyl-1, 3-propanediol amine, 2-amino-2-methyl-1-propanolamine, dimethylethanolamine, diethylaminoethanolamine, etc., and the carbon dioxide absorption rate is 99%. The organic absorbent has a strong absorption effect on carbon dioxide, and is beneficial to removing the carbon dioxide diffused from the anode, thereby promoting the reaction on the electrolysis side to move forward.
Alternatively, in other embodiments of the invention, where carbon dioxide is converted in a chemically catalyzed reduced form within a chemical conversion chamber, the solvent and chemical catalyst 6 fill the chemical conversion chamber 30 (as shown in FIG. 3), and the solvent is in a circulating state to promote dissolution of the carbon dioxide and contact with the chemical catalyst particles. Optionally, the solvent is an alcohol organic solvent, an amine organic solvent or water, wherein the alcohol organic solvent can be methanol, ethanol, ethylene glycol or the like, and the amine organic solvent can be monoethanolamine, diethanolamine, N-ethylethanolamine, 2-amino-2-methyl-1, 3-propanediol amine, 2-amino-2-methyl-1-propanediol amine, dimethylethanolamine, diethylaminoethanolamine or the like. Alternatively, the chemical catalyst has a particle size of 10-100 microns and a system solids content of 10-30%, which is advantageous for good dispersion of the chemical catalyst particles. The chemical catalyst 6 is a composite metal particle supported by an organic carrier or a composite metal particle supported by an inorganic carrier, such as a MOF-supported Cu nanoparticle, a zirconia-supported Cu-Zn nanoparticle, an alumina-supported Cu nanoparticle, a ceria-supported Cu nanoparticle, or the like. In some embodiments of the present invention, the chemical catalyst is preferably activated carbon supported Fe-Cu alloy nanoparticles having a particle size in the range of 5-20nm, a loading of 5-20%, a molar ratio of Fe to Cu of 5-20:95-80 parts; preferably, the Fe-Cu alloy loading amount in the activated carbon loaded Fe-Cu alloy nano particles is 10%, and the molar ratio of Fe to Cu is 10:90. in other embodiments of the present invention, the chemical catalyst is preferably activated carbon supported copper nanoparticles (commercially available) having a particle size in the range of 5-40nm and a loading of 5-60%; preferably, the copper nanoparticle loading in the activated carbon loaded copper nanoparticle is 40%. When carbon dioxide is converted in the chemical conversion chamber in the form of chemical catalytic reduction, the carbon dioxide conversion is 95%.
In some embodiments of the present invention, the method of preparing the composite metal particles supported by the organic porous support or the inorganic porous support of the chemical catalyst is a chemical coprecipitation method, and reference is specifically made to W.Wang, Z.Qu and L.Song et al, CO 2 hydrogenation to methanol over Cu/CeO 2 and Cu/ZrO 2 catalysts:Tuning methanol selectivity via metal-support interaction,Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.03.001。
Specifically, in analytical grade Ce (NO 3 ) 3 ·6H 2 O and Zr (NO) 3 ) 4 ·4H 2 O is a precursor, and an oxalate coprecipitation method is adopted to prepare CeO 2 And ZrO(s) 2 . Taking cerium oxide loaded Cu nano particles as an example, ceO 2 Is prepared by the following steps: ce (NO) 3 ) 3 ·6H 2 The solution of O is added into oxalate solution (such as 0.2mol/L potassium oxalate solution); stirring the mixture at 70 ℃ for 1h, and then aging for 2h; next, the precipitate was washed 3 times with deionized water and ethanol, dried overnight at 60℃in flowing air, and calcined at 550℃for 4 hours to give CeO 2 . Copper is deposited to CeO by a deposition-precipitation method 2 Cu (NO) 3 ) 2 ·3H 2 O as precursor, oxalate as precipitant (e.g. 0.2mol/L potassium oxalate solution) to deposit Cu-deposited CeO 2 Calcining the carrier for 4 hours at 450 ℃ to obtain the cerium oxide loaded Cu nano-particles. All chemical catalysts were calcined at 450℃for 4h.
Alternatively, in still other embodiments of the present invention, when carbon dioxide is converted in a photocatalytic reduced form within the chemical conversion chamber, the solvent and photocatalyst fills the chemical conversion chamber 30, and the solvent is in a circulating state, which may promote dissolution of the carbon dioxide and contact with the photocatalyst particles. Optionally, the solvent is an alcohol organic solventThe agent, amine organic solvent or water, wherein the alcohol organic solvent can be methanol, ethanol, glycol, etc., and the amine organic solvent can be monoethanolamine, diethanolamine, N-ethylethanolamine, 2-amino-2-methyl-1, 3-propanediol amine, 2-amino-2-methyl-1-propanediol amine, dimethylethanolamine, diethylaminoethanolamine, etc. Optionally, the photocatalyst has a particle size of 10-100 microns and a system solid content of 10-30%, which is favorable for good dispersion of the photocatalyst particles. The photocatalyst is a cocatalyst supported by a semiconductor material, wherein the semiconductor material comprises titanium dioxide and graphite phase carbon nitride (g-C) 3 N 4 ) Silicon carbide, zinc oxide, cadmium sulfide, etc.; the promoter may be simple substance of noble metal or non-noble metal such as gold, platinum, silver, ruthenium, copper, iron, lead, etc., oxide of noble metal or non-noble metal such as gold, platinum, silver, ruthenium, iron, lead, etc., sulfide of noble metal or non-noble metal such as gold, platinum, silver, copper, iron, lead, etc., halide nano material of noble metal or non-noble metal such as gold, platinum, silver, ruthenium, copper, iron, lead, etc., and molecular catalyst (such as porphyrin, pyridine, etc.) such as complex of noble metal or non-noble metal such as gold, platinum, silver, ruthenium, copper, iron, lead, etc. In some embodiments of the invention, the photocatalyst is preferably g-C 3 N 4 The load of the loaded cuprous oxide nanocrystalline catalyst is 5-80%; preferably, g-C 3 N 4 The loading of the cuprous oxide nanocrystalline in the loaded cuprous oxide nanocrystalline catalyst is 50%. In other embodiments of the present invention, the photocatalyst is preferably a titanium dioxide supported platinum catalyst having a platinum loading of 5 to 40%; preferably, the platinum loading in the titania-supported platinum catalyst is 20%. When carbon dioxide is converted in the chemical conversion chamber in the form of photocatalytic reduction, the carbon dioxide conversion is 95%.
In some embodiments of the invention, the photocatalyst semiconductor material supporting promoter is prepared by a thermochemical process. Wherein: g-C 3 N 4 The synthesis method of the organic semiconductor material can refer to g-C 3 N 4 Preparation method, synthesis method of inorganic semiconductor material such as zinc oxide and the like can be referred toThe chemical coprecipitation method of the chemical catalyst is carried out. The method for supporting all cocatalysts on semiconductor materials can be referred to as g-C 3 N 4 A preparation method of a supported cuprous oxide nanocrystalline catalyst.
Wherein g-C 3 N 4 The preparation method of the supported cuprous oxide nanocrystalline catalyst can refer to a reference Tian Zhiyuan. Monatom/nanoparticle @ g-C 3 N 4 Synthesis and photocatalytic research of composite catalytic System [ D]University of Tianjin, 2021.DOI:10.27360/d.cnki.gtlgy.2021.000188.
Wherein g-C 3 N 4 The preparation adopts a high-temperature calcination method, specifically: first, a certain amount of urea was added to a beaker containing 15 ml of water, and after waiting for the urea to dissolve, the mixture was stirred for 3 hours. The stirred urea solution is then subjected to rotary evaporation. After the spin-steaming was completed, the white solid was transferred from the flask to a porcelain boat. The porcelain boat was placed in a muffle furnace, and the temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute, and the temperature was kept constant at 500℃for 2 hours until the muffle furnace cooled to room temperature, to obtain a pale yellow solid (g-C) 3 N 4 ). The samples were washed three times with deionized water and dried in a vacuum oven.
Wherein g-C 3 N 4 The preparation of the cuprous oxide loaded nanocrystalline catalyst adopts an in-situ chemical synthesis method, specifically: the g-C synthesized above 3 N 4 First dispersed in 84mL of aqueous solution. Heating in water bath to 35deg.C, adding 5 mL of 0.1M CuCl 2 The solution was then vigorously stirred by the addition of 870mg of sodium dodecyl sulfate. After complete dissolution of the sodium lauryl sulfate, 1.8 mL of 1.0M sodium hydroxide solution was added and the solution was found to immediately turn bright blue, indicating the formation of copper hydroxide precipitate. At this time, 9.2mL of 0.1M NH was taken 2 OH HCl (hydroxylamine hydrochloride) was quickly injected into the solution within 5 s. Stirring for 1h in a water bath at 35℃and then washing with pure water and centrifuging to give a precipitate, which is then dried overnight in a vacuum oven at 45 ℃.
Optionally, in some embodiments of the present invention, an anolyte inlet, a catholyte outlet and a hydrogen outlet are disposed on a casing corresponding to the cathode chamber, where the catholyte inlet and the catholyte outlet are respectively connected to an outlet and an inlet of the alkaline aqueous solution storage tank, and circulation pumps are installed on connection pipes, so as to drive the alkaline aqueous solution to circulate in the anode chamber. The shell corresponding to the anode chamber is provided with an anode electrolyte inlet and an anode electrolyte outlet, wherein the anode electrolyte inlet and the anode electrolyte outlet are respectively communicated with the outlet and the inlet of the alkaline urea solution storage tank, and circulating pumps are arranged on communicating pipes so as to drive the alkaline urea solution to circularly flow in the anode chamber.
The working principle of the electrolytic cell for urea electrolysis hydrogen production and carbon reduction (namely the method for urea electrolysis hydrogen production and carbon reduction of the embodiment of the invention) is as follows:
specifically, the cathode chamber is used for electrolyzing alkaline aqueous solution to generate hydrogen evolution reaction to generate hydrogen and OH - The urea is converted into nitrogen, carbon dioxide and water, the nitrogen and the carbon dioxide enter a chemical conversion chamber through the anode, the nitrogen is discharged through a gas outlet of the chemical conversion chamber, and the carbon dioxide is converted into carbon monoxide, formic acid, formaldehyde, methanol or C in the chemical conversion chamber through chemical absorption, chemical catalytic reduction or photocatalytic reduction 2+ Hydrocarbon fuel, realizing zero carbon emission.
In summary, the electrolytic cell for hydrogen production and carbon reduction by urea electrolysis provided by the embodiment of the invention can lead carbon dioxide generated by urea electrolysis to be separated from an electrolytic anode chamber system in time in the reaction process and reduced to form a valuable product, thereby avoiding the problems of consumption of hydroxyl ions in an alkaline system by the carbon dioxide and pollution and blockage of a diaphragm by carbonate generated by the consumption of hydroxyl ions in the alkaline system, reducing the mixing pollution of the carbon dioxide to the hydrogen of the product, avoiding the release of the carbon dioxide and achieving the purpose of zero carbon emission.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. An electrolytic cell for producing hydrogen and reducing carbon by urea electrolysis is characterized by comprising a shell, a cathode chamber, an anode chamber and a chemical conversion chamber;
the shell is internally provided with a cathode, a diaphragm and an anode in sequence, and the cathode, the diaphragm and the anode are arranged in parallel; the anode is a gas diffusion electrode; the anode is connected with the positive electrode of the external power supply, and the cathode is connected with the negative electrode of the external power supply;
the cathode chamber is a closed chamber formed by sealing a cathode, a diaphragm and the inner wall of the shell; an alkaline aqueous solution is arranged in the cathode chamber;
the anode chamber is a closed chamber formed by sealing the diaphragm, the anode and the inner wall of the shell; an alkaline urea solution is arranged in the anode chamber;
the chemical conversion chamber is a closed chamber formed by sealing an anode and the inner wall of the shell; a carbon dioxide absorbent is arranged in the chemical conversion chamber; or a solvent and a chemical catalyst are arranged in the chemical conversion chamber; or a solvent and a photocatalyst are arranged in the chemical conversion chamber;
the method for producing hydrogen and reducing carbon by utilizing the electrolytic cell for producing hydrogen and reducing carbon by urea electrolysis comprises the following steps:
electrolyzing water in the cathode chamber to generate hydrogen;
electrolyzing the alkaline urea solution in an anode chamber to convert urea into nitrogen, carbon dioxide and water;
carbon dioxide in the anode chamber enters a chemical conversion chamber through the anode, and is converted into carbon monoxide, formic acid, formaldehyde, methanol or C in the chemical conversion chamber through chemical absorption, chemical catalytic reduction or photo catalytic reduction 2+ And (3) hydrocarbon fuel.
2. The electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to claim 1, wherein the cathode is a conductive substrate provided with a load layer on the surface; the conductive substrate is a metal plate or a porous plate; the material of the load layer is one or more than two of Pt, ru, rh, ir, ni, co, fe, zn, ti.
3. The electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to claim 1, wherein the membrane is a porous membrane or has OH - A conductive anion exchange membrane; the porous diaphragm is a Zirfon film; the anion exchange membrane is a polyarylether membrane, a polyethylene membrane, a polystyrene membrane, a polytetrafluoroethylene membrane or a polyphenyl membrane modified with cationic groups; the cationic group is a polyalkylammonium salt, an imidazole salt, a pyridine salt or a piperidine salt.
4. The electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to claim 1, wherein the anode is a porous substrate with an active catalytic layer supported on the surface; the porous matrix is foam metal or carbon material; the material of the active catalytic layer is one or more than two of Pt, ru, rh, ir, ni, co, fe, zn, ti.
5. The electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to claim 1, wherein the carbon dioxide absorbent fills the chemical conversion chamber; the carbon dioxide absorbent is an amine organic absorbent.
6. The electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to claim 1, wherein the solvent and chemical catalyst fill the chemical conversion chamber; the solvent is an alcohol organic solvent, an amine organic solvent or water; the chemical catalyst is composite metal particles supported by an organic porous carrier or composite metal particles supported by an inorganic porous carrier.
7. The electrolytic cell for urea electrolysis hydrogen production and carbon reduction according to claim 1, wherein the solvent and photocatalyst fill the chemical conversion chamber; the photocatalyst is a semiconductor material supported cocatalyst; the shell is made of light-transmitting materials.
8. The electrolytic cell for the electrolytic hydrogen production and carbon reduction of urea according to claim 7, wherein the solvent is an alcohol-based organic solvent, an amine-based organic solvent, or water; the photocatalyst is a cuprous oxide nanocrystalline catalyst loaded by graphite-phase carbon nitride.
9. The electrolytic cell for urea electrolytic hydrogen production and carbon reduction according to claim 1, wherein the circulating pumps are installed on both the liquid inlet communicating pipe and the liquid outlet communicating pipe of the chemical conversion chamber for driving the carbon dioxide absorbent or the solvent in the chemical conversion chamber to circulate.
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