EP3607111B1 - Zwei-membran-aufbau zur elektrochemischen reduktion von co2 - Google Patents

Zwei-membran-aufbau zur elektrochemischen reduktion von co2 Download PDF

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Publication number
EP3607111B1
EP3607111B1 EP18723765.6A EP18723765A EP3607111B1 EP 3607111 B1 EP3607111 B1 EP 3607111B1 EP 18723765 A EP18723765 A EP 18723765A EP 3607111 B1 EP3607111 B1 EP 3607111B1
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Prior art keywords
cathode
anode
space
exchange membrane
ion exchange
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German (de)
English (en)
French (fr)
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EP3607111A1 (de
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Bernhard Schmid
Christian Reller
Günter Schmid
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Siemens Energy Global GmbH and Co KG
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Siemens Energy Global GmbH and Co KG
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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
    • 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
    • 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
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • 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
    • 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
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms

Definitions

  • the present invention relates to an electrolysis cell comprising a cathode compartment comprising a cathode, a first ion exchange membrane which adjoins the cathode compartment, an anode compartment comprising an anode, and a second ion exchange membrane which adjoins the anode compartment, an electrolysis system comprising the electrolysis cell according to the invention, and a Method for the electrolysis of CO 2 using the electrolysis cell according to the invention or the electrolysis system according to the invention.
  • the CO 2 is converted into carbohydrates through photosynthesis. This process, which is broken down into many sub-steps in terms of time and space on a molecular level, is very difficult to copy on an industrial scale.
  • the currently more efficient way is the electrochemical reduction of the CO 2 s.
  • a hybrid form is the light-assisted electrolysis or the electrically assisted Photocatalysis. Both terms are to be used synonymously, depending on the perspective of the observer.
  • this process converts CO 2 into an energetically higher-value product such as CO, CH 4 , C 2 H 4 , etc. with the supply of electrical energy (possibly photo-assisted), which is obtained from regenerative energy sources such as wind or sun. converted.
  • the amount of energy required for this reduction ideally corresponds to the combustion energy of the fuel and should only come from renewable sources.
  • overproduction of renewable energies is not continuously available, but currently only at times with strong solar radiation and strong winds. However, this will increase in the near future with the further expansion of renewable energies.
  • Table 1 shows Faraday efficiencies FE (in [%]) of products that are produced during the reduction of carbon dioxide on various metal electrodes. The specified values apply to a 0.1 M potassium hydrogen carbonate solution as the electrolyte.
  • Electrolysis processes have developed significantly in the last few decades.
  • the PEM (proton exchange membrane; proton exchange membrane) water electrolysis could be optimized towards high current densities.
  • Large electrolysers with outputs in the megawatt range are already being launched on the market.
  • the US 2017/037522 A1 discloses an electrochemical device which converts carbon dioxide to a formic acid reaction product.
  • the CN 1 275 535 A discloses a method for the electrolytic separation of acid and alkali from waste acid and waste alkali
  • US Pat CN 104 593 810 A a process for the production of tetramethylammonium hydroxide by a bioelectrochemical system with continuous flow.
  • the electrolyser concept presented here represents a possible setup for CO 2 electrolysis, which is specifically designed to prevent salt encrustation on the cathode and CO 2 contamination of the anode exhaust gas. It is thus optimized for efficient material transport and long running times.
  • the inventors have developed concepts that are designed to specifically suppress known failure mechanisms.
  • the structures shown here enable the use of highly conductive electrolytes, which helps improve energy efficiency and space-time yield.
  • an electrolysis system which comprises the electrolysis cell according to the invention, a method for the electrolysis of CO 2 , an electrolysis cell according to the invention or an electrolysis system according to the invention being used, CO 2 being reduced at the cathode and hydrogen carbonate formed at the cathode through the first ion exchange membrane Salt bridge space moves, as well as the use of the electrolysis cell according to the invention or the electrolysis system according to the invention for the electrolysis of CO 2 .
  • FIGS 1 to 3 schematically show examples of electrolysis systems according to the invention with electrolysis cells according to the invention.
  • Figure 5 schematically shows a further example of an electrolysis system according to the invention with an electrolysis cell according to the invention.
  • Figure 6 is a schematic sketch to illustrate the functionality of a bipolar membrane.
  • Figures 7 and 8 show a graphic illustration of the advantages of a "zero gap" structure with regard to electrode shading by mechanical support structures.
  • FIGS 9 to 12 schematically show electrolysis equipment of comparative examples of the present invention.
  • Fig. 13 shows data of results obtained in Example 2.
  • Gas diffusion electrodes are electrodes in which liquid, solid and gaseous phases are present, and where in particular a conductive catalyst catalyzes an electrochemical reaction between the liquid and the gaseous phase.
  • hydrophobic is understood to be water-repellent. According to the invention, hydrophobic pores and / or channels are therefore those which repel water. In particular, according to the invention, hydrophobic properties are associated with substances or molecules with non-polar groups.
  • hydrophilic is understood to mean the ability to interact with water and other polar substances.
  • a basic anode reaction within the meaning of the invention is an anodic half-reaction in which cations are released that are not protons or deuterons.
  • Examples are the anodic decomposition of KCl or of KOH 2 KCl ⁇ 2e - + Cl 2 + 2K + 2 KOH ⁇ 4e - + O 2 + 2H 2 O + 4K +
  • An acidic anode reaction within the meaning of the invention is an anodic half-reaction in which protons or deuterons are released.
  • Examples are the anodic decomposition of HCl or H 2 O 2 HCl ⁇ 2e - + Cl 2 + 2H + 2 H 2 O ⁇ 4e - + O 2 + 4H +
  • Electro-osmosis is an electrodynamic phenomenon in which particles with a positive zeta potential are subjected to a force towards the cathode and all particles with a negative zeta potential are subjected to a force towards the anode. If a conversion takes place at the electrodes, i.e. if a galvanic current flows, there is also a flow of particles with a positive zeta potential to the cathode, regardless of whether the species is involved in the implementation or not. The same applies to a negative zeta potential and the anode. If the cathode is porous, the medium is also pumped through the electrode.
  • an electro-osmotic pump is an electrodynamic phenomenon in which particles with a positive zeta potential are subjected to a force towards the cathode and all particles with a negative zeta potential are subjected to a force towards the anode.
  • the material flows caused by electro-osmosis can also flow in the opposite direction to concentration gradients. Diffusion-related currents that compensate for the concentration gradients can thereby be overcompensated.
  • the material flows caused by the electro-osmosis can, in particular in the case of porous electrodes, lead to a flooding of areas that could not be filled by the electrolyte without an applied voltage. Therefore, this phenomenon can contribute to the failure of porous electrodes, particularly gas diffusion electrodes.
  • the cathode compartment, the first ion exchange membrane which contains an anion exchanger and which adjoins the cathode compartment, the anode compartment, the anode, the second ion exchange membrane which contains a cation exchanger and which adjoins the anode compartment, and the salt bridge compartment are not particularly restricted as long as the appropriate arrangement of these components is given in the electrolytic cell.
  • the salt bridge space is limited here by the first ion exchange membrane and the second ion exchange membrane and is furthermore not directly connected to the anode space, the anode, the cathode space and the cathode, so that an exchange of substances between the salt bridge space and the cathode space or the cathode is only possible via the first ion exchange membrane takes place and takes place between the salt bridge space and the anode space or the anode only via the second ion exchange membrane.
  • the cathode compartment, the anode compartment and the salt bridge compartment are not particularly restricted in terms of shape, material, dimensions, etc., provided they can accommodate the cathode, the anode and the first and second ion exchange membranes.
  • the three spaces can be formed, for example, within a common cell, in which case they can then be correspondingly separated by the first and the second ion exchange membrane.
  • feed and discharge devices for educts and products for example in the form of liquid, gas, solution, suspension, etc. can be provided, whereby these can also be returned if necessary.
  • feed and discharge devices for educts and products for example in the form of liquid, gas, solution, suspension, etc. can be provided, whereby these can also be returned if necessary.
  • feed and discharge devices for educts and products for example in the form of liquid, gas, solution, suspension, etc. can be provided, whereby these can also be returned if necessary.
  • Electrolysis of CO 2 - which can still contain CO, for example contains at least 20% by volume of CO 2 - this can be fed to the cathode in solution, as a gas, etc., for example in countercurrent to an electrolyte in the salt bridge space.
  • the respective feed can be provided both continuously and, for example, pulsed, etc., for which pumps, valves, etc. can be provided in an electrolysis system according to the invention, as well as cooling and / or heating devices in order to carry out correspondingly desired reactions at the anode and / or or to be able to catalyze cathode.
  • the materials of the respective rooms or the electrolysis cell and / or the other components of the electrolysis system can also be suitably adapted to the desired reactions, reactants, products, electrolytes, etc.
  • at least one power source per electrolysis cell is of course also included.
  • Further device parts that occur in electrolysis systems can also be provided in the electrolysis system or the electrolysis cell according to the invention.
  • the cathode can be adapted to a desired half-reaction, for example with regard to the reaction products.
  • the cathode comprises a metal selected from Cu, Ag, Au, Zn, and / or a salt thereof.
  • a cathode for reducing CO 2 and possibly CO can comprise a metal such as Cu, Ag, Au, Zn, etc. and / or a salt thereof, with suitable materials being able to be adapted to a desired product.
  • the catalyst can thus be selected depending on the desired product. In the case of the reduction of CO 2 to CO, for example, the catalyst is preferably based on Ag, Au, Zn and / or their compounds such as Ag 2 O, AgO, Au 2 O, Au 2 O 3 , ZnO.
  • Cu or Cu-containing compounds such as Cu 2 O, CuO and / or copper-containing mixed oxides with other metals, etc., are preferred.
  • the corresponding cathodes can here also contain materials customary in cathodes, such as binders, ionomers, for example anion-conductive ionomers, fillers, etc., which are not particularly restricted.
  • the cathode comprises a hydrophilic additive selected from TiO 2 , Al 2 O 3 , MgO 2 , polysulfones, polyimides, polybenzoxazoles, and polyether ketones.
  • the cathode can also, according to certain embodiments, at least one ionomer, for example an anion-conductive ionomer (e.g. anion exchange resin, which e.g.
  • a, for example, conductive, carrier material for example a metal such as titanium
  • a non-metal such as carbon, Si, boron nitride (BN), boron-doped diamond, etc.
  • a conductive oxide such as indium tin oxide (ITO), aluminum zinc oxide (AZO) or fluorinated tin oxide (FTO) - for example for the production of photoelectrodes, and / or at least one polymer based on polyacetylene, polyethoxythiophene, polyaniline or polypyrrole, for example in polymer-based electrodes; non-conductive supports such as polymer networks are possible, for example, if the conductivity of the catalyst layer is sufficient), binders (e.g.
  • hydrophilic and / or hydrophobic polymers e.g. organic binders, e.g. selected from PTFE (polytetrafluoroethylene), PVDF (polyvinylenedifluoride), PFA (perfluoroalkoxy polymers), FEP (fluorinated ethylene-propylene copolymers), PFSA (perfluorosulfonic acid polymers), and mixtures thereof, in particular PTFE), conductive fillers (eg carbon), and / or non-conductive fillers (eg glass), which are not particularly restricted. It contains hydrophilic additives selected from TiO 2 , Al 2 O 3 , MgO 2 , polysulfones, for example polyphenyl sulfones, polyimides, polybenzoxazoles or polyether ketones.
  • organic binders e.g. selected from PTFE (polytetrafluoroethylene), PVDF (polyvinylenedifluoride), PFA (perfluoroal
  • the cathode in particular in the form of a gas diffusion electrode, contains an anion-conductive component.
  • the anode is not particularly restricted and can be adapted to a desired half-reaction, for example with regard to the reaction products.
  • the oxidation of a substance takes place in the anode space.
  • the material of the anode is not particularly limited and depends primarily on the desired reaction. Exemplary anode materials include platinum or platinum alloys, palladium or palladium alloys, and vitreous carbon.
  • anode materials are also conductive oxides such as doped or undoped TiO 2 , indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), iridium oxide, etc. If necessary, these catalytically active compounds can only be applied to the surface using thin-film technology be, for example on a titanium and / or carbon support.
  • the anode catalyst is not particularly limited. IrO x (1.5 ⁇ x ⁇ 2) or RuO 2 , for example, are also used as a catalyst for O 2 or Cl 2 generation.
  • catalysts based on Fe-Ni or Co-Ni can also be used to generate O 2.
  • the structure described below with a bipolar membrane or bipolar membrane is suitable for this.
  • the corresponding anodes can also contain the usual materials in anodes, such as binders, ionomers, for example also cation-conducting ionomers, for example containing tertiary amine groups, alkylammonium groups and / or phosphonium groups), fillers, hydrophilic additives, etc., which are not particularly restricted, which, for example, also above are described with respect to the cathodes.
  • binders ionomers, for example also cation-conducting ionomers, for example containing tertiary amine groups, alkylammonium groups and / or phosphonium groups
  • fillers for example containing tertiary amine groups, alkylammonium groups and / or phosphonium groups
  • hydrophilic additives etc.
  • the electrodes mentioned above by way of example can be combined with one another as desired.
  • the first ion exchange membrane which contains an anion exchanger and which adjoins the cathode space, is not particularly restricted according to the invention. It can contain, for example, an anion exchanger in the form of an anion exchange layer, in which case further layers such as non-ion-conducting layers can then be included.
  • the first ion exchange membrane is an anion exchange membrane, that is, for example, an ion-conductive membrane (or also in the broader sense a membrane with a cation exchange layer) with positively charged functionalizations, which is not particularly restricted.
  • a preferred charge transport takes place in the anion exchange layer or an anion exchange membrane through anions.
  • the first ion exchange membrane is used in particular and therein in particular an anion exchange layer or an anion exchange membrane for providing an anion transport along fixed, fixed positive charges.
  • an electrolyte into the cathode which is promoted by electro-osmotic forces, can be reduced or completely avoided.
  • a suitable first ion exchange membrane for example anion exchange membrane, shows good wettability by water and / or aqueous salt solutions, high ion conductivity and / or a tolerance of the functional groups contained therein to high pH values, in particular shows no Hoffmann elimination.
  • An exemplary AEM according to the invention is the A201-CE membrane used in the example and sold by Tokuyama, the "Sustainion” sold by Dioxide Materials or an anion exchange membrane sold by Fumatech, such as Fumasep FAS-PET or Fumasep FAD-PET.
  • a suitable second ion exchange membrane for example a cation exchange membrane or a bipolar membrane, contains a cation exchanger which can be in contact with the electrolyte in the salt bridge space. Otherwise, the second ion exchange membrane, which contains a cation exchanger and which adjoins the anode space, is not particularly restricted. It can contain, for example, a cation exchanger in the form of a cation exchange layer, in which case further layers such as non-ion-conducting layers can be included. It can also be designed as a bipolar membrane or as a cation exchange membrane (CEM).
  • the cation exchange membrane or cation exchange layer is, for example, an ion-conductive membrane or ion-conductive layer with negatively charged functionalizations.
  • a preferred charge transport into the salt bridge takes place in the second ion exchange membrane by means of cations.
  • commercially available Nafion® membranes are suitable as CEM, or those sold by Fumatech Fumapem-F membranes, the Aciplex sold by Asahi Kasei, or the Flemion membranes sold by AGC.
  • other polymer membranes modified with strongly acidic groups groups such as sulfonic acid, phosphonic acid
  • the second ion exchange membrane prevents the transfer of anions, in particular HCO 3 - , into the anode space.
  • anions in particular HCO 3 -
  • a suitable second ion exchange membrane for example cation exchange membrane, shows good wettability by water and aqueous salt solutions, high ion conductivity, stability towards reactive species that can be generated at the anode (for example given for perfluorinated polymers, and / or stability in the required pH regimes, depending on the anode reaction.
  • the first ion exchange membrane and / or the second ion exchange membrane are hydrophilic.
  • the anode and / or cathode are at least partially hydrophilic.
  • the first ion exchange membrane and / or the second ion exchange membrane can be wetted with water. In order to ensure good ion conductivity of the ionomers, swelling with water is preferred. Experiments have shown that poorly wettable membranes can lead to a significant deterioration in the ionic connection of the electrodes.
  • the anode and / or cathode have sufficient hydrophilicity. If necessary, this can be adapted by means of hydrophilic additives such as TiO 2 , Al 2 O 3 , or other electrochemically inert metal oxides, etc. and is adapted to the cathode.
  • the salt bridge space is not particularly limited insofar as it is arranged between the first ion exchange membrane and the second ion exchange membrane.
  • the cathode is designed as a gas diffusion electrode, as a porous bonded catalyst structure, as a particulate catalyst on a support, as a coating of a particulate catalyst on the first ion exchange membrane, as a porous conductive support in which a catalyst is impregnated, or as a non-closed flat structure which (r / s) contains an anion exchange material.
  • the anode is designed as a gas diffusion electrode, as a porous bonded catalyst structure, as a particulate catalyst on a support, as a coating of a particulate catalyst on the second ion exchange membrane, as a porous conductive support in which a catalyst is impregnated, or as a non-closed flat structure, which (r / s) contains a cation exchange material.
  • the various embodiments of the cathode and anode can be combined with one another as desired.
  • FIG. 1 to 4 Exemplary different modes of operation of a double membrane cell are shown in Figures 1 to 4 shown - in Figures 1 to 3 also in connection with further components of an electrolysis system according to the invention, also with regard to the method according to the invention.
  • a CO 2 reduction to CO is assumed as an example.
  • the process is not restricted to this reaction but can also be used for any other products, such as hydrocarbons, preferably gaseous ones.
  • Fig. 1 shows an example of a 2-membrane structure for CO 2 -electro-reduction with an acidic anode reaction
  • Fig. 2 a 2-membrane structure for CO 2 -electro-reduction with a basic anode reaction
  • Fig. 3 an experimental setup for a double membrane cell, as it is also used in example 1 according to the invention.
  • the cathode K is provided in the cathode space I and the anode A in the anode space III, with a salt bridge space II being formed between these spaces, which is connected to the cathode space I by a first membrane, here as AEM, and the anode space III by a second Membrane, here as CEM, is separated.
  • AEM first membrane
  • CEM second Membrane
  • Fig. 4 shows a further structure of an electrolysis cell in which both the first ion exchange membrane, which is designed as an anion exchange membrane AEM, and the second ion exchange membrane, which is designed as a cation exchange membrane CEM, are not in direct contact with the cathode K or the anode A, respectively are.
  • the cathode and the anode can be designed as full electrodes, which is not according to the invention.
  • the electrolytic cell shown in FIG Figures 1 to 3 Electrolysis systems shown are used.
  • the different half-cells can also be made from Figures 1 to 3 , as well as the correspondingly arranged components of the electrolysis system, can be combined as desired, as well as with other electrolysis half-cells (not shown).
  • the second ion exchange membrane is designed as a bipolar membrane, with an anion exchange layer of the bipolar membrane preferably facing towards the anode space and a cation exchange layer of the bipolar membrane towards the salt bridge space. This is particularly advantageous when using aqueous electrolytes, as discussed below.
  • FIG. 5 shows an example of a 2-membrane structure for CO 2 -electro-reduction with AEM on the cathode side and bipolar membrane (CEM / AEM) on the anode side, here as in FIG Figures 1 to 3 the supply of catholyte k, salt bridge s (electrolyte for the salt bridge space) and anolyte a, as well as a return R of CO 2 , is shown and an example of oxidation of water takes place on the anode side.
  • the other reference symbols correspond to those in Figs. 1 to 4 .
  • a structure is also possible in which a bipolar membrane is used as the second ion exchange membrane.
  • a bipolar membrane is, for example, a sandwich of a CEM and an AEM. Usually, however, it is not a question of two membranes placed one on top of the other, but rather a membrane with at least two layers.
  • the representation in Figures 5 and 6 with AEM and CEM only serves to illustrate the preferred orientation of the layers.
  • the AEM or anion exchange layer points towards the anode, the CEM or cation exchange layer towards the cathode.
  • These membranes are almost impassable for both anions and cations.
  • the conductivity of a bipolar membrane is therefore not based on the transport capacity for ions. Instead, ion transport usually occurs through acid-base disproportionation of water in the middle of the membrane. This generates two oppositely charged charge carriers that are transported away by the E-field.
  • the OH - ions generated in this way can be conducted through the AEM part of the bipolar membrane to the anode, where they are oxidized 40H - ⁇ O 2 + 2H 2 O + 4e - and the "H + " ions through the CEM part of the bipolar membrane into the salt bridge or salt bridge space II, where they can be neutralized by the cathodically generated HCO 3 - ions.
  • a structure can also be implemented for a basic anode reaction that does not require constant supply and removal of salts or anode products. Otherwise, this is only possible when using anolytes based on acids with electrochemically inactive anions such as H 2 SO 4 .
  • hydroxide electrolytes such as KOH or NaOH can also be used. High pH values thermodynamically favor water oxidation and allow the use of much cheaper anode catalysts, for example iron-nickel-based, which would not be stable in acidic conditions.
  • Figure 6 shows in detail a sketch to illustrate the mode of operation of a bipolar membrane with the blocking of anions A - and cations C + .
  • the anode contacts the second ion exchange membrane and / or according to certain embodiments the cathode contacts the first ion exchange membrane, as already described above by way of example. This enables a good connection to the salt bridge area. Electrical shadowing effects can also be reduced or even avoided.
  • both the anode and the cathode are connected directly to the first or second ion exchange membrane, for example each comprising a polymer electrolyte. This could prevent shadowing effects from mechanical support structures in the electrolyte chambers. If non-conductive support structures lie directly on the electrochemically active surfaces, they are isolated from the ion transport and are inactive. However, the first and second ion exchange membranes are preferably on the full surface and thus create a full-surface ionic connection of the catalyst.
  • FIGS 7 and 8 graphically illustrate the advantages of such a "zero-gap" structure with regard to electrode shading by mechanical support structures, with FIG Figure 7 the catalyst 1 of the electrode (active) and the mechanical support structure 4 are shown between which points of the polymer electrolyte 3 with little ion current are formed by the liquid electrolyte 5 in a polymer electrolyte 2 as ion exchange material, while in FIG Figure 8 inactive catalyst 6 is shown on the mechanical support structure 4.
  • the anode and / or the cathode are contacted with a conductive structure on the side facing away from the salt bridge space.
  • the conductive structure is not particularly limited here.
  • the anode and / or the cathode are contacted by conductive structures from the side facing away from the salt bridge. These are not particularly limited. This can be, for example, carbon tiles, metal foams, metal knitted fabrics, expanded metals, graphite structures or metal structures.
  • the present invention relates to an electrolysis system, comprising the electrolysis cell according to the invention, further comprising a return device, which is connected to a discharge of the salt bridge space and a feed to the cathode space, which is set up to produce an educt of the cathode reaction that is formed in the salt bridge space can lead back into the cathode compartment.
  • a return device which is connected to a discharge of the salt bridge space and a feed to the cathode space, which is set up to produce an educt of the cathode reaction that is formed in the salt bridge space can lead back into the cathode compartment.
  • the electrolysis system comprises a return device, which is connected to a discharge of the salt bridge space and a feed to the cathode space, which is set up to return an educt of the cathode reaction, which can be formed in the salt bridge space, to the cathode space.
  • a return device which is connected to a discharge of the salt bridge space and a feed to the cathode space, which is set up to return an educt of the cathode reaction, which can be formed in the salt bridge space, to the cathode space.
  • the present invention relates to a method for the electrolysis of CO 2 , using an electrolysis cell or an electrolysis system according to the invention, with CO 2 being reduced at the cathode and hydrogen carbonate formed at the cathode through the first ion exchange membrane to an electrolyte walks in the salt bridge area. A further transition of this hydrogen carbonate into the anolyte can be prevented by the second ion exchange membrane.
  • the electrolysis cell according to the invention or the electrolysis system according to the invention are used in the method according to the invention for the electrolysis of CO 2 , which is why aspects which are discussed in connection with these above and below also relate to this method.
  • CO 2 is electrolyzed, although it is not excluded that on the cathode side, in addition to CO 2 , another starting material such as CO is also present, which can also be electrolyzed, i.e. a mixture is present that includes CO 2 and, for example, CO.
  • a mixture is present that includes CO 2 and, for example, CO.
  • an educt contains at least 20% by volume of CO 2 on the cathode side.
  • an electrolyte in the salt bridge space, which can ensure the electrolytic connection between the cathode space and the anode space.
  • This electrolyte is also referred to as a salt bridge and is not particularly restricted according to the invention provided it is a, preferably aqueous, solution of salts.
  • the salt bridge is in this case an electrolyte, preferably with high ionic conductivity, and is used to establish contact between anode and cathode. According to certain embodiments, the salt bridge also enables the dissipation of waste heat. In addition, the salt bridge serves as a reaction medium for the anodically and cathodically generated charge carriers. According to certain embodiments, the salt bridge is a solution of one or more salts, also referred to as conductive salts, which are not particularly restricted. According to certain embodiments, the salt bridge has a buffer capacity which is sufficient to deal with pH fluctuations during operation and the establishment of pH gradients within the cell dimensions to suppress.
  • the pH value of the 1: 1 buffer should preferably be in the neutral range in order to achieve the highest possible capacity at the neutral pH values given by the CO 2 / hydrogen carbonate system. Accordingly, the hydrogen phosphate / dihydrogen phosphate buffer, for example, which has a 1: 1 pH value of 7.2, would be suitable. Furthermore, salts are preferably used in the salt bridge, which do not damage the electrodes in the event of trace diffusion through the membranes.
  • the chemical nature of the salt bridge electrolyte is much less restricted than with other cell concepts.
  • salts that would damage the electrodes such as halides (chloride, bromides ⁇ damage to Ag or Cu cathodes; fluorides ⁇ damage to Ti anodes) or that would be electrochemically converted by the electrodes, e.g. nitrates or oxalates, can be used . Since the ion transport into the electrodes can be prevented, higher concentrations can also be used. Overall, a high conductivity of the salt bridge can thus be guaranteed, which leads to an improvement in energy efficiency.
  • electrolytes can also be present in the anode compartment and / or cathode compartment, which are also referred to as anolyte or catholyte, but according to the invention it is not excluded that there are no electrolytes in the two spaces and, accordingly, only liquids or gases for conversion into these are supplied, for example only CO 2 , possibly also as a mixture with, for example, CO, to the cathode and / or water or HCl to the anode.
  • an anolyte and / or catholyte are present, which can be the same or different and can differ from or correspond to the salt bridge, for example with regard to the conductive salts contained, solvents, etc.
  • a catholyte here is the electrolyte flow around the cathode and, according to certain embodiments, serves to supply the cathode with substrate or educt.
  • the following embodiments are possible, for example.
  • the catholyte can, for example, be in the form of a solution of the substrate (CO 2 ) in a liquid carrier phase (e.g. water), optionally with conductive salts, which are not restricted, or as a mixture of the substrate with other gases (e.g. water vapor + CO 2 ).
  • the substrate can also be present as a pure phase, for example CO 2. If uncharged liquid products arise during the reaction, these can be washed out by the catholyte and can then optionally be separated off accordingly.
  • An anolyte is an electrolyte flow around the anode and, according to certain embodiments, serves to supply the anode with substrate or educt and, if necessary, to transport away anode products.
  • the following embodiments are possible, for example.
  • the salt bridge and, if applicable, the anolyte and / or catholyte are aqueous electrolytes, with the anolyte and / or catholyte optionally being added with corresponding starting materials which are converted at the anode or cathode.
  • the addition of educt is not particularly restricted.
  • CO 2 can be added to a catholyte outside the cathode space, or can also be added through a gas diffusion electrode, or can also be fed to the cathode space only as a gas. Similar considerations are possible for the anode compartment, depending on the starting material used, for example water, HCl, etc., and the desired product.
  • the salt bridge space comprises an electrolyte containing hydrogen carbonate.
  • Hydrogen carbonate can also be produced here, for example, by a reaction of CO 2 and water at the cathode, as will be explained further below.
  • the hydrogen carbonate can, for example, form a salt with cations present in the salt bridge space , for example alkali metal cations such as K +. This is particularly the case in the case of a basic anode reaction, in which the alkali metal cations such as K + are continuously fed from the anode compartment.
  • the resulting hydrogen carbonate salt can thus be concentrated to above the saturation concentration, so that it can be deposited in the salt bridge reservoir, if necessary, and can then be separated off.
  • An anion exchange layer or AEM prevents salinisation of the cathode. Salt crystallization in the salt bridge space should preferably be avoided. According to certain embodiments, the electrolyte can be cooled, for example after leaving the cell, in order to initiate crystallization in the reservoir and thus lower its concentration.
  • excess hydrogen carbonate in the salt bridge can be decomposed into CO 2 and water by the protons escaping from the anode space.
  • the electrolyte of the salt bridge space does not include an acid.
  • the generation of hydrogen at the cathode can be reduced or prevented.
  • the generation of hydrogen is not preferred, since it is more energy-efficient with pure hydrogen electrolysers because it can be generated with a lower overvoltage. If necessary, it can be accepted as a by-product.
  • the anode compartment does not contain any hydrogen carbonate. This can prevent the release of CO 2 in the anode compartment. This can be an undesirable one Avoid entangling the anode products with CO 2 .
  • an anode gas that is to say a gaseous anode product, and CO 2 are released separately.
  • An electrolysis cell according to the invention or a method in which it is used, for example the method according to the invention for the electrolysis of CO 2 is characterized by the introduction of two ion-selective membranes and a salt bridge space that enables a third electrolyte flow, the salt bridge, which leads to bounded on both sides by one of the membranes.
  • AEM AEM
  • CEM CEM
  • FIG. 1 to 4 Exemplary different modes of operation of a double membrane cell are shown in Figures 1 to 4 shown - in Figures 1 to 3 also in connection with further components of an electrolysis system according to the invention, also with regard to the method according to the invention.
  • a CO 2 reduction to CO is assumed as an example. In principle, however, the process is not limited to this reaction, but rather can also be used for any other products, preferably gaseous.
  • Fig. 1 shows an example of a 2-membrane structure for CO 2 -electro-reduction with an acidic anode reaction
  • Fig. 2 a 2-membrane structure for CO 2 -electro-reduction with a basic anode reaction
  • Fig. 3 an experimental setup for a double membrane cell, as it is also used in example 1 according to the invention
  • Fig. 4 also shows a further structure of an electrolysis cell in which both the first ion exchange membrane, which is designed as an anion exchange membrane AEM, and the second anion exchange membrane, which is designed as a cation exchange membrane CEM, are not in direct contact with the cathode K or the anode A, respectively are.
  • the cathode and the anode can be designed as full electrodes, although this is not according to the invention.
  • the electrolytic cell shown in FIG Figures 1 to 3 Electrolysis systems shown are used.
  • the different half-cells can also be made from Figures 1 to 3 , as well as the correspondingly arranged components of the electrolysis system, can be combined as desired, as well as with other electrolysis half-cells (not shown).
  • the salt can be precipitated in a controlled manner, for example in a cooled crystallizer.
  • the composition of the salt bridge can be selected according to certain embodiments so that the hydrogen carbonate of the cation generated at the anode is the component with the lowest solubility.
  • a corresponding method is, for example, in WO 2017/005594 described.
  • salts are preferably used in the salt bridge, which do not damage the electrodes in the event of trace diffusion through the membranes.
  • K + for example, could be used as Salt bridge KF or KHCO 3 itself can be used close to the saturation concentration or a mixture of both salts.
  • anionic products such as formate or acetate are formed in the given reaction, these are also transported away by the salt bridge and, according to certain embodiments, can be separated off by a suitable device.
  • the present invention relates to the use of an electrolysis cell according to the invention or an electrolysis system according to the invention for the electrolysis of CO 2 .
  • the method according to the invention is a high pressure electrolysis.
  • Figure 9 shows a two-chamber structure with an AEM as a membrane, the reference numerals being those of Figures 1 to 4 correspond.
  • both can be prevented on the anode side by the second membrane, which comprises a cation exchanger, for example a cation-selective membrane.
  • Figure 10 shows a two-chamber structure with a CEM as a membrane, the reference numerals being those of FIG Figures 1 to 4 correspond.
  • the construction shown provides an adaptation of a PEM (proton exchange membrane) electrolyzer for hydrogen production is, since it contains a CEM there is no loss of CO 2 over the anode gas as the CEM the migration of HCO 3 - ions. can prevent the anolyte.
  • PEM proto exchange membrane
  • the ionic connection of the cathode can, however, be problematic.
  • a large part of the charge transport would take place through cations such as K + , which cannot be converted in the cathode. This can lead to an accumulation of hydrogen carbonates in the cathode, which can ultimately fail and block the gas transport.
  • KOH + CO 2 ⁇ KHCO 3 In the case of an acidic anode reaction, protons are transported to the cathode. Since CEMs are modified with strongly acidic groups, the pH value at the cathode is very low, which can be disadvantageous for CO 2 reduction due to competing H 2 development.
  • Figure 11 shows a three-chamber structure with a CEM as a membrane, the reference numerals being those of FIG Figures 1 to 4 correspond.
  • the in Figure 11 The setup shown is used, for example, in chlor-alkali electrolysis. It differs from the present 2-membrane structure primarily through the lack of AEM. Also an analogue to Fig. 3 without AEM is possible.
  • electro-osmosis can become a problem in the case of CO 2 conversion. Since cations in particular have positive zeta potentials, they are pumped through the cathode into the catholyte chamber I during operation. There you form KHCO 3 .
  • the charge transport of cations is "in a dead end run" towards HCO 3 by introducing an AEM - ions displaced, which can be transported through the salt bridge.
  • the advantage of the 2-membrane structure shown here is the suppression of the electroosmotic pumping out of cations in the catholytes, which favors the use of highly concentrated electrolytes and high current densities. At the same time, contamination of the anode gas by CO 2 can be prevented.
  • Figure 12 shows a two-chamber structure with a bipolar membrane as the membrane, the reference numerals being those of FIG Figures 1 to 4 correspond.
  • Bipolar membranes are also being discussed for CO 2 electrolysis. In principle, this is a combination of a CEM and an AEM, as explained above. In contrast to the solution discussed here, however, there is no salt bridge between the membranes, and the membrane components are oriented inversely to the present invention: CEM to the cathode, AEM to the anode.
  • FIG Figure 3 An electrolysis system according to the invention was constructed as shown in FIG Figure 3 realized on a laboratory scale. The functionality of the cell was successfully demonstrated on a laboratory scale.
  • A201-CE (Tokuyama) and Nafion N117 (DuPont) were used as AEM and CEM.
  • 2M KHCO 3 served as the salt bridge.
  • 2.5M aqueous KOH and water-saturated CO 2 served as anolyte and catholyte.
  • a titanium sheet coated with iridium mixed oxide was used as the anode. The anode was not directly connected to the CEM in this case. Chamber III was between the anode and the CEM, as shown.
  • a commercial carbon-gas diffusion layer (Freudenberg H2315 C2) which was coated with a copper-based catalyst and the anion-conductive ionomer AS-4 (Tokuyama) served as the cathode. It was directly on the AEM.
  • Example 2 comparative example and example 3 (not according to the invention):
  • Example 2 The setup from Example 1 was compared with a further setup in which there was no cathode-AEM composite.
  • the rest of the structure corresponded to that of Example 1, a silver cathode being used as the cathode (Example 2).
  • a test setup corresponding to Example 1 was used, but a silver cathode was used as the cathode (Example 3).
  • Fig. 13 shows the comparison of two chromatograms from Example 3 and Example 2. These were recorded under identical conditions: same current density, silver cathode, approximately the same Faraday efficiency (95% for CO) and the same CO 2 excess.
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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK3453065T3 (da) 2016-05-03 2021-05-17 Opus 12 Incorporated Reaktor med avanceret arkitektur til elektrokemisk reduktion af cox
DE102017208610A1 (de) 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
DE102018212409A1 (de) 2017-11-16 2019-05-16 Siemens Aktiengesellschaft Kohlenwasserstoff-selektive Elektrode
DE102017223521A1 (de) 2017-12-21 2019-06-27 Siemens Aktiengesellschaft Durchströmbare Anionentauscher-Füllungen für Elektrolytspalte in der CO2-Elektrolyse zur besseren räumlichen Verteilung der Gasentwicklung
JP7364313B2 (ja) 2018-01-22 2023-10-18 トゥエルブ ベネフィット コーポレーション 二酸化炭素リアクタ制御のための方法
DE102018111275A1 (de) * 2018-05-11 2019-11-14 Deutsches Zentrum für Luft- und Raumfahrt e.V. Elektrochemischer Reaktor und Verfahren zum Erzeugen von Ammoniak und Wasserstoff aus einer Harnstofflösung durch Elektrolyse
DE102018210303A1 (de) 2018-06-25 2020-01-02 Siemens Aktiengesellschaft Elektrochemische Niedertemperatur Reverse-Watergas-Shift Reaktion
CA3120748A1 (en) * 2018-11-28 2020-06-04 Opus 12 Incorporated Electrolyzer and method of use
US20200216968A1 (en) * 2019-01-07 2020-07-09 Opus 12 Inc. System and method for methane production
DE102019201153A1 (de) * 2019-01-30 2020-07-30 Siemens Aktiengesellschaft Verfahren zur energieeffizienten Herstellung von CO
US11702753B2 (en) * 2019-07-09 2023-07-18 University Of Alaska Fairbanks Apparatus for the electrolytic production of hydrogen, oxygen, and alkalinized seawater
BR112022010144A2 (pt) 2019-11-25 2022-09-06 Twelve Benefit Corp Conjunto de eletrodos de membrana para redução de cox
DE102020204224A1 (de) 2020-04-01 2021-10-07 Siemens Aktiengesellschaft Vorrichtung und Verfahren zur Kohlenstoffdioxid- oder Kohlenstoffmonoxid-Elektrolyse
EP3926075A1 (en) * 2020-06-19 2021-12-22 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Method for electrochemical production of a product in a cell comprising a polyelectrolyte
JP7247150B2 (ja) * 2020-09-02 2023-03-28 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
CN113430547B (zh) * 2021-05-06 2023-07-25 盐城工学院 一种电解二氧化碳制甲酸钾的装置及电解方法
CN113403637A (zh) * 2021-05-31 2021-09-17 中国科学院金属研究所 pH不对称成对电合成体系及其应用
US20230010993A1 (en) * 2021-07-12 2023-01-12 Dioxycle Carbon dioxide extraction electrolysis reactor
CN113943942B (zh) * 2021-11-09 2022-10-28 深圳先进技术研究院 新能源电能驱动的二氧化碳储能系统和储能方法
CN114457359B (zh) * 2021-12-24 2024-03-19 苏州思萃同位素技术研究所有限公司 利用离子交换膜制备卤化氘的装置及卤化氘的制备方法
CN114369842B (zh) * 2022-01-25 2023-10-27 太原师范学院 一种羰基化合物催化加氢装置及其应用
CN114540838A (zh) * 2022-03-25 2022-05-27 昆明理工大学 一种在微间隙电解池中制备一氧化碳和次氯酸盐的隔膜电解方法
WO2023201039A1 (en) * 2022-04-14 2023-10-19 William Marsh Rice University Electrochemical carbon dioxide capture and recovery in a solid electrolyte reactor system
WO2024078866A1 (en) 2022-10-13 2024-04-18 Totalenergies Onetech Co2 electroreduction to multi-carbon products in acidic conditions coupled with co2 regeneration from carbonate

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357217A (en) * 1981-10-02 1982-11-02 Occidental Research Corporation Three compartment electrolytic cell method for producing hydrogen peroxide
EP0612864B1 (en) * 1993-02-26 1999-05-06 Permelec Electrode Ltd. Electrolytic cell and processes for producing alkali hydroxide and hydrogen peroxide
CN1117034C (zh) * 2000-01-24 2003-08-06 黄君礼 酸/碱电解分离装置
BR0314724A (pt) * 2002-09-27 2005-07-26 Bayer Materialscience Ag Processo para preparação de um eletrodo de difusão gasosa
GB2396625A (en) * 2002-12-28 2004-06-30 Accentus Plc Removal of an acid
US9481939B2 (en) 2010-07-04 2016-11-01 Dioxide Materials, Inc. Electrochemical device for converting carbon dioxide to a reaction product
US9815021B2 (en) * 2010-03-26 2017-11-14 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
US10047446B2 (en) * 2010-07-04 2018-08-14 Dioxide Materials, Inc. Method and system for electrochemical production of formic acid from carbon dioxide
US9145615B2 (en) 2010-09-24 2015-09-29 Yumei Zhai Method and apparatus for the electrochemical reduction of carbon dioxide
US8529758B2 (en) * 2011-03-22 2013-09-10 Dionex Corporation CO2-removal device and method
ITMI20110500A1 (it) * 2011-03-29 2012-09-30 Industrie De Nora Spa Cella per l elettrodialisi depolarizzata di soluzioni saline
CN102181876B (zh) * 2011-03-30 2012-12-19 昆明理工大学 一种电化学催化还原二氧化碳制备一氧化碳的方法与装置
FR2988405B1 (fr) * 2012-03-26 2015-04-10 Rhodia Operations Cathode pour la reduction du co2 par electrocatalyse
CN102912374B (zh) * 2012-10-24 2015-04-22 中国科学院大连化学物理研究所 一种以双极膜为隔膜的电化学还原co2电解池及其应用
US9695050B2 (en) * 2012-11-02 2017-07-04 Terra Co2 Technologies Ltd. Methods and systems using electrochemical cells for processing metal sulfate compounds from mine waste and sequestering CO2
CN104593810A (zh) * 2014-12-20 2015-05-06 中山大学 一种连续流生物电化学系统制备四甲基氢氧化铵的方法
JP2016157893A (ja) 2015-02-26 2016-09-01 東京エレクトロン株式会社 カーボン膜の成膜方法および成膜装置
DE102015212504A1 (de) 2015-07-03 2017-01-05 Siemens Aktiengesellschaft Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung
DK3325692T3 (da) * 2015-07-22 2020-10-19 Coval Energy Ventures B V Fremgangsmåde og reaktor til elektrokemisk reduktion af carbondioxid
DE102015215309A1 (de) 2015-08-11 2017-02-16 Siemens Aktiengesellschaft Präparationstechnik von kohlenwasserstoffselektiven Gasdiffusionselektroden basierend auf Cu-haltigen-Katalysatoren
US10344388B2 (en) * 2015-09-16 2019-07-09 Kabushiki Kaisha Toshiba CO2 reduction catalyst, CO2 reduction electrode, CO2 reduction reaction apparatus, and process for producing CO2 reduction catalyst
DK3453065T3 (da) * 2016-05-03 2021-05-17 Opus 12 Incorporated Reaktor med avanceret arkitektur til elektrokemisk reduktion af cox
US11091846B2 (en) * 2016-06-24 2021-08-17 Stichting Wageningen Research Electrochemical process and reactor
EP3260578A1 (en) * 2016-06-24 2017-12-27 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Hydrogen peroxide production
CN106552497B (zh) * 2016-11-25 2019-02-01 东南大学 一种用于二氧化碳捕集和提纯的装置及方法
DE102017208610A1 (de) 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
DE102017211930A1 (de) * 2017-07-12 2019-01-17 Siemens Aktiengesellschaft Membran gekoppelte Kathode zur Reduktion von Kohlendioxid in säurebasierten Elektrolyten ohne mobile Kationen
DE102017223521A1 (de) * 2017-12-21 2019-06-27 Siemens Aktiengesellschaft Durchströmbare Anionentauscher-Füllungen für Elektrolytspalte in der CO2-Elektrolyse zur besseren räumlichen Verteilung der Gasentwicklung
DE102018202184A1 (de) * 2018-02-13 2019-08-14 Siemens Aktiengesellschaft Separatorlose Doppel-GDE-Zelle zur elektrochemischen Umsetzung

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