EP4435149A2 - Kohlendioxidelektrolysevorrichtung und verfahren zur elektrolyse von kohlendioxid - Google Patents

Kohlendioxidelektrolysevorrichtung und verfahren zur elektrolyse von kohlendioxid Download PDF

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Publication number
EP4435149A2
EP4435149A2 EP23196520.3A EP23196520A EP4435149A2 EP 4435149 A2 EP4435149 A2 EP 4435149A2 EP 23196520 A EP23196520 A EP 23196520A EP 4435149 A2 EP4435149 A2 EP 4435149A2
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European Patent Office
Prior art keywords
acid
carbon dioxide
anode
cathode
flow path
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English (en)
French (fr)
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EP4435149A3 (de
Inventor
Maki Yonetsu
Yuki Kudo
Ryota Kitagawa
Satoshi Mikoshiba
Akihiko Ono
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Toshiba Corp
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Toshiba Corp
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Publication of EP4435149A2 publication Critical patent/EP4435149A2/de
Publication of EP4435149A3 publication Critical patent/EP4435149A3/de
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • Arrangements disclosed herein relate to a carbon dioxide electrolytic device and a method of electrolyzing carbon dioxide.
  • a CO 2 electrolytic device that reduces carbon dioxide (CO 2 ) generated from a power plant, an incinerator, or the like.
  • a CO 2 electrolytic device includes a cathode (reduction electrode) that reduces CO 2 to produce a carbon compound such as carbon monoxide (CO), and an anode (oxidation electrode) that oxidizes water (H 2 O) or hydroxide ions (OH - ).
  • a cell structure in which the cathode and the anode are stacked with a separator such as an ion exchange membrane or a porous membrane interposed therebetween, and direct supply of CO 2 to a cathode catalyst layer of the electrolysis cell allows a reduction reaction of CO 2 to rapidly progress.
  • a porous base of the anode (oxidation electrode) uses titanium (Ti) as a material having low chemical reactivity and high conductivity.
  • Ti titanium
  • a subject be solved by the aspect of the present invention is to provide a carbon dioxide electrolytic device and a method of electrolyzing carbon dioxide capable of preventing a characteristic deterioration and the like of an electrolysis cell by preventing elution and the like of an anode.
  • a carbon dioxide electrolytic device and a method of electrolyzing carbon dioxide capable of preventing a characteristic deterioration and the like of an electrolysis cell by preventing elution and the like of an anode.
  • a carbon dioxide electrolytic device of an arrangement includes: an electrolysis cell including a cathode configured to reduce carbon dioxide to produce a carbon compound, an anode configured to oxidize water or hydroxide ion to produce oxygen and having a base containing titanium, a cathode flow path configured to supply carbon dioxide to the cathode, an anode flow path configured to supply an electrolytic solution containing water to the anode, and a separator configured to separate the anode and the cathode; a gas supply unit configured to supply carbon dioxide to the cathode flow path; at least one of a humidifier configured to humidify carbon dioxide supplied to the cathode flow path by using a humidification water, and a liquid pouring part configured to add the humidification water to the carbon dioxide; and an electrolytic solution supply unit configured to supply the electrolytic solution to the anode flow path.
  • At least one of the electrolytic solution and the humidification water contains an oxidant; and/or the carbon dioxide gas supplied to the cathode flow path contains at least one selected from a group consisting of nitrogen dioxide, nitrogen monoxide, and ozone.
  • FIG. 1 is a sectional view illustrating a first example of a carbon dioxide (CO 2 ) electrolytic device 10 of the arrangement.
  • FIG. 2 is a sectional view illustrating a second example of the carbon dioxide (CO 2 ) electrolytic device 10 of the arrangement.
  • the CO 2 electrolytic device 10 illustrated in FIG. 1 and FIG. 2 includes an electrolysis cell 20.
  • the electrolysis cell 20 includes a cathode part 30, an anode part 40, and a separator 50 disposed to separate these.
  • the cathode part 30 includes a reduction electrode (cathode) 31 having a metal catalyst layer, a cathode flow path 32, and a cathode current collector 33.
  • the cathode flow path 32 is a gas flow path that supplies a CO 2 gas to the cathode 31, and is formed of a pit (groove) provided in a cathode flow path plate 34.
  • the cathode 31 is disposed to be in contact with CO 2 flowing through the cathode flow path 32.
  • the anode part 40 includes an anode (oxidation electrode) 41, an anode flow path 42, and an anode current collector 43.
  • the anode flow path 42 is an electrolytic solution flow path that supplies an electrolytic solution as an anode solution to the anode 41, and is formed of a pit (groove) provided in an anode flow path plate 44.
  • the anode 41 is disposed to be in contact with the anode solution flowing through the anode flow path 42.
  • the CO 2 electrolytic device 10 includes a gas supply unit 60 that supplies CO 2 to the electrolysis cell 20, and an anode solution supply unit (supply system) 70 that supplies the anode solution to the electrolysis cell 20.
  • the gas supply unit 60 includes a CO 2 storage part 61 such as a CO 2 gas cylinder, a humidification water supply part that supplies a humidification water to the CO 2 gas, and a gas addition part 63 that adds an additive gas to the CO 2 gas.
  • the electrolytic device 10 illustrated in FIG. 1 includes a humidification part 62 that humidifies the CO 2 gas, as the humidification water supply part.
  • the gas supply unit 60 supplies the humidified CO 2 gas to the cathode flow path 32 via a gas pipe 64.
  • the CO 2 gas supplied to the cathode flow path 32 is not limited to a single gas of CO 2 , and may also be gas mainly composed of CO 2 (for example, gas containing CO 2 of 90 vol% or more).
  • ions are supplied via the separator 50, and the CO 2 gas is supplied from the cathode flow path 32.
  • a CO 2 reduction product is discharged mainly from the cathode flow path 32.
  • the electrolytic solution supply unit 70 includes an anode solution tank 71, a pump 72, an anode solution concentration measurement part 73, and an oxidant supply part 74, and supplies the anode solution to the anode flow path 42 from the anode solution tank 71 via the pump 72 and an electrolytic solution pipe 75.
  • the anode solution circulates through the anode flow path 42 and the electrolytic solution pipe 75.
  • the cathode current collector 33 and the anode current collector 43 in the CO 2 electrolytic device 10 are connected to a power supply 80.
  • anode flow path plate 44 forming the anode flow path 42, and the cathode flow path plate 34 forming the cathode flow path 32 a material having low chemical reactivity and having high conductivity is preferably used.
  • a metal material such as Ti or SUS, carbon, or the like.
  • the electrolysis cell 20 is sandwiched by a pair of support plates (not illustrated), and further tightened by bolts or the like.
  • the power supply 80 connected to the cathode current collector 33 and the anode current collector 43 is not limited to an ordinary commercial power supply, a battery, or the like, and may be a power supply that converts renewable energy into electric energy and supplies it.
  • a power supply that converts kinetic energy or potential energy such as wind power, water power, geothermal power or tidal power into electric energy
  • a power supply like a solar cell such as a photoelectric conversion element that converts light energy into electric energy
  • a power supply such as a fuel cell or a storage battery that converts chemical energy into electric energy
  • a power supply such as a device that converts vibrational energy such as sound into electric energy.
  • renewable energy is preferable in terms of the environment since it also enables effective use of carbon dioxide.
  • the cathode 31 is an electrode (reduction electrode) that causes a reduction reaction of carbon dioxide (CO 2 ) to produce a carbon compound such as carbon monoxide (CO), methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), methanol (CH 3 OH), ethanol (C 2 H 5 OH), or ethylene glycol (C 2 H 6 O 2 ).
  • a side reaction in which hydrogen (H 2 ) is produced by a reduction reaction of water (H 2 O) is sometimes caused simultaneously with the reduction reaction of carbon dioxide (CO 2 ).
  • the cathode 31 has a first surface in contact with the separator 50, and a second surface facing the cathode flow path 32. The first surface of the cathode 31 is in contact with one surface of the separator 50.
  • the cathode flow path 32 being a flow path of the gas containing CO 2 (hereinafter, also described as a CO 2 gas) is formed of a pit (groove portion/recessed portion) provided in the cathode flow path plate 34.
  • the cathode flow path plate 34 is provided with gas introduction port and discharge port, whose illustration is omitted.
  • the CO 2 gas is introduced from the gas supply unit 60 via the gas introduction port or the gas discharge port. Further, a reaction product gas containing CO, H 2 , or the like is discharged via the gas introduction port or the gas discharge port, and the discharged gas is sent to a not-illustrated valuable manufacturing part or collected by a product collecting part.
  • the cathode flow path plate 34 and the cathode flow path 32 provided in the cathode flow path plate 34 are provided to be in contact with the second surface on a side opposite to the first surface that is in contact with the separator 50, of the cathode 31.
  • the cathode 31 has a structure capable of making ions and water move between the separator 50 and the cathode flow path 32, for example, a porous structure of a mesh material, a punched material, a porous body, a metal fiber sintered body, or the like.
  • the cathode catalyst material may have nanoparticles, a nanostructure, a nanowire, or the like for the purpose of increasing the reduction reaction.
  • the nanostructure is a structure having nanoscale irregularities on a surface of the catalyst material and the like.
  • the cathode 31 has a porous gas diffusion base and a porous cathode catalyst layer, for example.
  • a porous layer denser than the gas diffusion base may be disposed.
  • the gas diffusion base is disposed on the cathode flow path 32 side, and the cathode catalyst layer is disposed on the separator 50 side.
  • the cathode catalyst layer may enter the gas diffusion layer.
  • the cathode 31 has a porous structure.
  • the cathode catalyst layer preferably has catalyst nanoparticles, a catalyst nanostructure, or the like.
  • the gas diffusion base is constituted of, for example, carbon paper, carbon cloth, or the like, and is preferably subjected to water repellent treatment.
  • the cathode catalyst layer is supplied with ions from the anode 41 via the separator 50.
  • the CO 2 gas is supplied and a product obtained by the reduction reaction of the CO 2 gas is discharged.
  • the reduction reaction of CO 2 occurs at a three-phase boundary of the cathode catalyst layer, and a gaseous product is discharged from the cathode flow path 32.
  • the cathode catalyst layer of the cathode 31 is preferably constituted of a catalyst material (cathode catalyst material) capable of reducing CO 2 to produce a carbon compound and capable of reducing an overvoltage in the above reaction.
  • a catalyst material capable of reducing CO 2 to produce a carbon compound and capable of reducing an overvoltage in the above reaction.
  • the cathode catalyst material there can be cited a metal such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), titanium (Ti), cadmium (Cd), zinc (Zn), indium (In), gallium (Ga), lead (Pb), or tin (Sn), a metal material such as an alloy or an intermetallic compound containing at least one of the above metals, a carbon material such as carbon (C), graphene, CNT (carbon nanotube), fullerene, or ket
  • the anode 41 is an electrode (oxidation electrode) that causes an oxidation reaction of water (H 2 O) in the anode solution to produce oxygen (O 2 ) and hydrogen ions (H + ), or causes an oxidation reaction of hydroxide ions (OH - ) produced in the cathode part 30 to produce oxygen and water.
  • the anode 41 is disposed between the separator 50 and the anode flow path 42 to be in contact with them. More specifically, the anode 41 has a first surface in contact with the separator 50, and a second surface facing the anode flow path 42. The first surface of the anode 41 is in close contact with the separator 50.
  • a solution inlet port and a solution outlet port are connected to the anode flow path plate 44, and via these solution inlet port and solution outlet port, the anode solution is introduced and discharged by the pump 72.
  • the anode solution flows through the inside of the anode flow path 42 so as to be brought into contact with the anode 41.
  • the anode current collector 43 is in electrical contact with a surface on a side opposite to the anode 41, of the anode flow path plate 44 that forms the anode flow path 42.
  • the anode 41 is preferably composed mainly of a catalyst material (anode catalyst material) capable of oxidizing water (H 2 O) to produce oxygen and hydrogen ions or oxidizing hydroxide ions (OH - ) to produce water and oxygen, and capable of reducing an overvoltage in the above reaction.
  • a catalyst material anode catalyst material capable of oxidizing water (H 2 O) to produce oxygen and hydrogen ions or oxidizing hydroxide ions (OH - ) to produce water and oxygen, and capable of reducing an overvoltage in the above reaction.
  • a metal such as platinum (Pt), palladium (Pd), or nickel (Ni), an alloy or an intermetallic compound containing the above metal, a binary metal oxide such as a manganese oxide (Mn-O), an iridium oxide (Ir-O), a nickel oxide (Ni-O), a cobalt oxide (Co-O), an iron oxide (Fe-O), a tin oxide (Sn-O), an indium oxide (In-O), a ruthenium oxide (Ru-O), a lithium oxide (Li-O), or a lanthanum oxide (La-O), a ternary metal oxide such as Ni-Co-O, Ni-Fe-O, La-Co-O, Ni-La-O, or Sr-Fe-O, a quaternary metal oxide such as Pb-Ru-Ir-O or La-Sr-Co-O, or a metal complex such as a Ru complex or an Fe complex.
  • a binary metal oxide such as a manga
  • the anode 41 includes a base (porous base) having a structure capable of moving the anode solution and ions between the separator 50 and the anode flow path 42, for example, a porous structure such as a mesh material, a punched material, or a porous sintered body.
  • the porous base is preferably composed of Ti or a Ti alloy having low reactivity.
  • the oxide is used as the anode catalyst material, it is preferable to form a catalyst layer by attaching or staking the anode catalyst material on the surface of the porous base composed of the metal material containing Ti described above.
  • the anode catalyst material preferably has a shape of a nanoparticle, a nanostructure, a nanowire, or the like in order to enhance the oxidation reaction.
  • the nanostructure is a structure having nanoscale irregularities on the surface of the catalyst material.
  • an aqueous solution containing an arbitrary electrolyte can be used.
  • the aqueous solution containing the electrolyte there can be cited, for example, an aqueous solution containing a phosphate ion (PO 4 2- ), a borate ion (BO 3 3- ), a sodium ion (Na + ), a potassium ion (K + ), a calcium ion (Ca 2+ ), a lithium ion (Li + ), a cesium ion (Cs + ), a magnesium ion (Mg 2+ ), a chloride ion (Cl - ), a hydrogen carbonate ion (HCO 3 - ), a carbonate ion (CO 3 2- ), or the like.
  • a pH of the anode solution is not particularly limited, but it is preferably 6 or more and 10 or less when considering use environments.
  • the anode solution is more preferably an alkaline solution containing HCO 3 - , CO 3 2- , LiHCO 3 , NaHCO 3 , KHCO 3 , or the like.
  • the separator 50 is composed of a material capable of moving ions between the anode 41 and the cathode 31, and capable of separating the anode part 40 and the cathode part 30, and is formed of, for example, a porous membrane made an organic polymeric material, an ion exchange membrane, or the like.
  • the organic material forming the porous membrane used for the separator 50 is not limited in particular, and examples thereof include a fluorocarbon resin such as Teflon (registered trademark), hydrocarbon polymers such as polyether, polysulfone, polyethylene, and polypropylene, cellulose, and the like.
  • ion exchange membrane there can be cited, for example, a cation exchange membrane such as Nafion (registered trademark) or Flemion (registered trademark), or an anion exchange membrane such as Neosepta (registered trademark), Selemion (registered trademark), Sustainion (registered trademark), or PiperION (registered trademark).
  • a cation exchange membrane such as Nafion (registered trademark) or Flemion (registered trademark)
  • an anion exchange membrane such as Neosepta (registered trademark), Selemion (registered trademark), Sustainion (registered trademark), or PiperION (registered trademark).
  • the supplied CO 2 gas may be supplied in a dry state, but is more preferably humidified. This can prevent drying of the membrane when the ion exchange membrane is used for the separator 50. Further, when the porous membrane made of the organic polymeric material is used for the separator 50, by using a CO 2 gas in a humidified state, a wet seal is formed on the porous membrane made of the organic polymeric material. Such a wet seal can prevent a crossover between the anode part 40 and the cathode part 30, namely, a to-and-fro movement of gas and liquid between the anode part 40 and the cathode part 30 and a reaction of mutual gasses caused by the movement.
  • the gas supply unit 60 includes the humidification part 62 that humidifies the CO 2 gas flowing through the gas pipe 64.
  • the humidification part (humidification device) 62 includes a humidification water tank, for example, and is configured to humidify the CO 2 gas by vaporizing the humidification water by using an ultrasonic oscillator or the like.
  • the gas supply unit 60 includes the liquid pouring part (liquid pouring pipe) 65 that adds the humidification water to the CO 2 gas flowing through the gas pipe 64.
  • the carbon compound as the reduction product of carbon dioxide is not limited to carbon monoxide, and may be methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), methanol (CH 3 OH), ethanol (C 2 H 5 OH), ethylene glycol (C 2 H 6 O 2 ), or the like, and furthermore, carbon monoxide being a reduction product may be further reduced to produce the organic compounds described above.
  • H + produced in the anode moves in the electrolytic solution that exists in the anode 41 and the separator 50, and reaches the vicinity of the cathode 31.
  • the reduction reaction of carbon dioxide (CO 2 ) is caused by electrons (e - ) based on the current supplied from the power supply 80 to the cathode 31 and H + moved to the vicinity of the cathode 31.
  • CO 2 supplied from the cathode flow path 32 to the cathode 31 is reduced to produce CO.
  • hydrogen ions (H + ) receive electrons, thereby producing hydrogen. At this time, hydrogen may be produced simultaneously with carbon monoxide. 2CO 2 + 4H + + 4e - ⁇ 2CO + 2H 2 O ... (2) 2H + + 2e - ⁇ H 2 ... (3)
  • hydroxide ions (OH - ) produced by these reactions diffuse in the vicinity of the anode 41, and as presented in the following formula (6), the hydroxide ions (OH - ) are oxidized to produce oxygen (O 2 ).
  • O 2 oxygen
  • Such a carbon dioxide electrolytic device 10 of the arrangement is not specialized in only the reduction of carbon dioxide, but it can produce carbon monoxide and hydrogen at 1:2, and produce a carbon dioxide reduction product and hydrogen at such an arbitrary ratio as to produce methanol in a chemical reaction thereafter, for example.
  • Hydrogen is a material that is inexpensive and easy to obtain through the electrolysis of water and from fossil fuel, so that a ratio of hydrogen is not required to be large. From these viewpoints, it is preferable that a ratio of carbon monoxide to hydrogen is at least 1 or more, and desirably 1.5 or more, in terms of economical and environmental viewpoints.
  • Ti or the Ti alloy is used for the porous base of the anode 41.
  • the metal material containing Ti is known as a material having low chemical reactivity and excellent corrosion resistance.
  • the porous base made of the metal material containing Ti is likely to be subjected to elution and the like caused by the alkaline electrolytic solution.
  • the elution of Ti in the porous base causes clogging of pores of the porous base. This prevents passage of the gas and the electrolytic solution in the anode 41 and a reaction based thereon.
  • the elution of Ti caused by the alkaline electrolytic solution becomes a main cause of deteriorating not only characteristics of the anode 41 but also characteristics of the electrolysis cell 20.
  • the carbon dioxide electrolytic device 10 of the arrangement in order to prevent the elution of Ti being a part of the composing material of the anode 41, caused by the alkaline electrolytic solution or the like, at least one selected from a configuration (1), a configuration (2), and a configuration (3) described below is adopted. At this time, any one of the configuration (1), the configuration (2), and the configuration (3) may be adopted, or two or more of the above configurations may be adopted in combination.
  • Configuration (2) An oxidant is added to the humidification water that humidifies the CO 2 gas.
  • Configuration (3) At least one selected from a group consisting of nitrogen dioxide (NO 2 ), nitrogen monoxide (NO), and ozone (O 3 ) is added to the CO 2 gas.
  • an oxidizing acid and hydrogen peroxide there can be cited an oxidizing acid and hydrogen peroxide.
  • the oxidizing acid there can be cited at least one selected from nitric acid, perchloric acid, chloric acid, chlorous acid, hypochlorous acid, chromic acid, dichromic acid, permanganic acid, arsenic acid, selenic acid, bromic acid, and iodic acid. These are capable of oxidizing a member that is in contact therewith, and thus can prevent the elution of Ti when the anode 41 containing Ti, for example, is brought into contact with the alkaline electrolytic solution.
  • hydrogen peroxide H 2 O 2
  • the prevention of Ti elution may be performed by not only the addition of the oxidant in a liquid state such as the oxidizing acid or hydrogen peroxide to the liquid such as the anode solution or the humidification water, but also the addition of gas such as NO 2 , NO, or O 3 to the CO 2 gas, as described in the configuration (3).
  • gas such as NO 2 , NO, or O 3 to the CO 2 gas, as described in the configuration (3).
  • NO 2 or NO is added to the CO 2 gas, it is converted into an oxidizing nitric acid (NHO 3 ).
  • NHO 3 oxidizing nitric acid
  • a concentration of the oxidant added to the anode solution and the humidification water is preferably 0.1 mM or more and 100 mM (millimoles per liter) or less. If the concentration of the oxidant is less than 0.1 mM, there is a possibility that the effect of preventing the elution of Ti cannot be obtained sufficiently. Further, if the concentration of the oxidant exceeds 100 mM, there is a possibility that an adverse effect is exerted on the original characteristics of the anode solution and the humidification water. The concentration of the oxidant is more preferably 0.1 mM or more and 50 mM or less.
  • the concentration of the oxidant in the electrolytic solution and the humidification water it is possible to measure the types and the concentrations of various acids by an ion chromatography of solution, for example. The measurement can be performed in a similar manner in both a case where a measuring object is the electrolytic solution and a case where the measuring object is the humidification water.
  • a gas concentration of at least one of NO 2 , NO, and O 3 in the CO 2 gas is 10 ppb or more and 1000 ppm or less. If the above-described gas concentration is less than 10 ppb, there is a possibility that the effect of preventing the elution of Ti cannot be obtained sufficiently. Further, if the above-described gas concentration exceeds 1000 ppm, there is a possibility that an adverse effect is exerted on the characteristics of the CO 2 gas.
  • the above-described gas concentration in the CO 2 gas is more preferably 100 ppb or more and 100 ppm or less.
  • NO 2 , NO, and NO x in the gas it is possible to perform trace measurement of NO and NO 2 by a high-sensitive NO x analyzer for atmosphere (Model 42i-TL) manufactured by Thermo Fisher Scientific Inc., or the like, using a reduced-pressure chemiluminescence method, for example. It is possible to design such that an adjustment gas before being introduced into the cell is collected in a bag and the gas is introduced into a device to perform concentration measurement, or the gas is branched off from the middle of the pipe to be measured.
  • ozone concentration in the gas it is possible to measure the ozone concentration in the gas by a high-precision ozone gas concentration meter using an ultraviolet absorption method, for example, ozone mate (OZG-3300/3500), or the like.
  • an ultraviolet absorption method for example, ozone mate (OZG-3300/3500), or the like.
  • the oxidant is added to the humidification water based on a measurement result obtained by a humidification water concentration measurement part that is provided according to need, so that the concentration of the oxidant in the humidification water satisfies the above-described range.
  • the humidification water is required to be replenished since it decreases during an operation, and when performing the replenishment, the humidification water with adjusted oxidant concentration may be added, or the concentration may be measured in the anode solution concentration measurement part 73 to adjust an introduction amount of the oxidant.
  • the humidification water concentration measurement part may be provided or may not be provided.
  • the carbon dioxide electrolytic device 10 of the arrangement it is possible to prevent the elution of Ti when the anode 41 containing Ti is brought into contact with the alkaline electrolytic solution, by adding the oxidant to the anode solution, adding the oxidant to the humidification water that humidifies the CO 2 gas, or adding at least one selected from a group consisting of NO 2 , NO, and O 3 to the CO 2 gas. Therefore, it becomes possible to prevent clogging of pores due to the elution of the porous base containing Ti of the anode 41, the deterioration of characteristics of the anode 41 caused thereby, and the deterioration of characteristics of the electrolysis cell 20 as well.
  • the characteristics of the electrolysis cell 20 can be maintained over a long period of time.
  • catalytic particles in which Au nanoparticles (metal catalyst) each having an average diameter of 2 nm were supported on carbon particles, and a Nafion solution (product name, manufactured by Du Pont) as an ion-conductive material (ion-exchange resin) were prepared.
  • the materials, pure water, and isopropanol were mixed at a predetermined ratio, to thereby prepare a catalyst coating solution.
  • an electrode in which a Ti nonwoven fabric was coated thereon with IrO 2 nanoparticles serving as a catalyst was used.
  • This IrO 2 /Ti nonwoven fabric was cut into 4 ⁇ 4 cm to obtain the anode.
  • a porous membrane of polyethersulfone was used as a separator.
  • the anode current collector and the cathode current collector were connected to an external power supply, an electrolytic solution added with nitric acid of 3 millimoles per liter (mM) (a pH of the electrolytic solution when starting measurement was 7.5 to 8.5) was made to flow through the anode solution flow path, and a CO 2 gas was made to flow through a cathode gas flow path, to thereby fabricate a carbon dioxide electrolytic device illustrated in FIG. 1 .
  • Electrolysis cells and electrolytic devices illustrated in FIG. 1 or FIG. 2 were fabricated in a manner similar to that in the example 1, except that conditions described in Table 1 (the destination to which the additive was added, the type of additive and the added amount, and the pH of the electrolytic solution when starting measurement) were respectively adopted.
  • An electrolysis cell and an electrolytic device illustrated in FIG. 1 were fabricated in a manner similar to that in the example 1, except that no nitric acid was added to the electrolytic solution in the example 1.
  • a carbon dioxide electrolytic device comprising:
  • Clause 2 The device according to clause 1, wherein the oxidant is at least one selected from a group consisting of an oxidizing acid and hydrogen peroxide.
  • Clause 3 The device according to clause 2, wherein the oxidizing acid includes at least one selected from a group consisting of nitric acid, perchloric acid, chloric acid, chlorous acid, hypochlorous acid, chromic acid, dichromic acid, permanganic acid, arsenic acid, selenic acid, bromic acid, and iodic acid.
  • Clause 4 The carbon dioxide electrolytic device according to any one of clause 1 to clause 3, wherein a concentration of the oxidant in the electrolytic solution or the humidification water is 0.1 mM or more and 100 mM or less.
  • Clause 5 The device according to clause 1, wherein a concentration of at least one selected from the group consisting of nitrogen dioxide, nitrogen monoxide, and ozone in the carbon dioxide gas is 10 ppb or more and 1000 ppm or less.
  • Clause 6 The device according to any one of clause 1 to clause 5, wherein the electrolytic solution has a pH of 6 or more and 10 or less.
  • Clause 7 The device according to any one of clause 1 to clause 6, further comprising a measurement part configured to measure a concentration of the oxidant in the electrolytic solution or the humidification water.
  • Clause 8 The device according to any one of clause 1 to clause 7, wherein the separator includes a porous membrane.
  • a carbon dioxide electrolytic device comprising:
  • a carbon dioxide electrolytic device comprising:
  • Clause 12 A method of electrolyzing carbon dioxide, comprising:
  • Clause 13 The method according to clause 12, wherein the oxidant is at least one selected from a group consisting of an oxidizing acid and hydrogen peroxide.
  • Clause 14 The method according to clause 13, wherein the oxidizing acid includes at least one selected from a group consisting of nitric acid, perchloric acid, chloric acid, chlorous acid, hypochlorous acid, chromic acid, dichromic acid, permanganic acid, arsenic acid, selenic acid, bromic acid, and iodic acid.
  • Clause 15 The method according to any one of clause 12 to clause 14, wherein to the electrolytic solution or the humidification water, the oxidant is added at a concentration of 0.1 mM or more and 100 mM or less.
  • Clause 16 The method according to clause 12, wherein to the carbon dioxide gas, at least one selected from the group consisting of nitrogen dioxide, nitrogen monoxide, and ozone is added at a concentration of 10 ppb or more and 1000 ppm or less.
  • Clause 17 The method according to any one of clause 12 to clause 16, wherein the electrolytic solution has a pH of 6 or more and 10 or less.
  • Clause 18 A method of electrolyzing carbon dioxide, comprising:
  • Clause 19 A method of electrolyzing carbon dioxide, comprising:
  • Clause 20 A method of electrolyzing carbon dioxide, comprising:

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP23196520.3A 2023-03-23 2023-09-11 Kohlendioxidelektrolysevorrichtung und verfahren zur elektrolyse von kohlendioxid Pending EP4435149A3 (de)

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JP2023134597A JP2024137606A (ja) 2023-03-23 2023-08-22 二酸化炭素電解装置及び二酸化炭素電解方法

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FR2999612B1 (fr) * 2012-12-17 2015-02-20 Commissariat Energie Atomique Procede d'electrolyse a haute temperature de la vapeur d'eau et d'un autre gaz, interconnecteur, reacteur et procedes de fonctionnement associes
JP6951309B2 (ja) * 2018-09-18 2021-10-20 株式会社東芝 二酸化炭素電解装置および二酸化炭素電解方法
EP3670700A1 (de) * 2018-12-19 2020-06-24 Paris Sciences et Lettres - Quartier Latin Verfahren zur umwandlung von kohlendioxid (co2) in synthesegas durch eine elektrolysereaktion
BR112023016931A2 (pt) * 2021-02-23 2023-11-07 Twelve Benefit Corp Procedimento de recuperação para eletrolisadores de óxido de carbono
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AU2023229473B2 (en) 2025-07-03

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