WO2019215309A1 - Réacteur électrochimique et procédé de production d'ammoniac et d'hydrogène à partir d'une solution d'urée par électrolyse - Google Patents

Réacteur électrochimique et procédé de production d'ammoniac et d'hydrogène à partir d'une solution d'urée par électrolyse Download PDF

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Publication number
WO2019215309A1
WO2019215309A1 PCT/EP2019/061996 EP2019061996W WO2019215309A1 WO 2019215309 A1 WO2019215309 A1 WO 2019215309A1 EP 2019061996 W EP2019061996 W EP 2019061996W WO 2019215309 A1 WO2019215309 A1 WO 2019215309A1
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Prior art keywords
exchange membrane
cathodic
anodic
catalyst layer
electrochemical reactor
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PCT/EP2019/061996
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German (de)
English (en)
Inventor
Seyed Schwan Hosseiny
Jens Mitzel
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Deutsches Zentrum für Luft- und Raumfahrt e.V.
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Priority to EP19724765.3A priority Critical patent/EP3791011A1/fr
Publication of WO2019215309A1 publication Critical patent/WO2019215309A1/fr

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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
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2882—Catalytic reactors combined or associated with other devices, e.g. exhaust silencers or other exhaust purification devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/04—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an electric, e.g. electrostatic, device other than a heater
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/25—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an ammonia generator
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/34—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an electrolyser
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/40—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a hydrolysis catalyst
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to an electrochemical reactor for generating ammonia and hydrogen from a urea solution by electrolysis, which electrochemical reactor comprises an anode and a cathode separated by an ion exchange membrane.
  • the present invention relates to a method for producing ammonia and hydrogen from a urea solution by electrolysis, in which method an anode and a cathode separated by an ion exchange membrane are used.
  • the invention relates to a system for the exhaust gas treatment of combustion devices, in particular of internal combustion engines, comprising a reducing agent generating device for generating a reducing agent from an exhaust gas treatment agent.
  • a major disadvantage of the type of exhaust gas treatment described is the removal of nitrogen oxides at low temperatures, in particular during the starting phase of internal combustion engines, which can take up to ten minutes. During this period, the currently available on the market exhaust treatment systems using urea solutions can not be turned on. The reason for this is that the thermal reactors for urea cleavage only work efficiently above 500 ° C. Operation at lower temperatures is not possible because the reactors clog due to the low decomposition rate and the urea polymerizes. The exhaust treatment system would come to a standstill.
  • the ammonia required for the reduction of nitrogen oxides is produced, on the other hand hydrogen.
  • hydrogen can react with nitrogen monoxide and oxygen to form molecular nitrogen and water.
  • electrochemical reactors to produce ammonia and hydrogen from a urea solution by electrolysis also poses problems.
  • Known electrochemical reactors with ion exchange membranes are currently used either with cation exchange membranes or with anion exchange membranes. By selecting the respective membrane, the milieu of the same is given either in the acidic or in the alkaline range. It is therefore the same on both sides of the ion exchange membrane. In other words, the milieus of both sides, so the cathode side and the anode side of the electrochemical reactor, coupled together.
  • urea electrolyzer systems which can be used for the exhaust gas treatment of internal combustion engines, in which urea solutions having a pH of at least 13 must be used in order to achieve the desired reactions, namely the splitting of urea into ammonia and the simultaneous production to reach from hydrogen.
  • KOH potassium hydroxide
  • Potassium hydroxide is highly corrosive, so that its handling can be done only by qualified personnel.
  • these solutions have a creep property, which significantly complicates the sealing of the electrolyzer systems.
  • the ion exchange membrane is designed in the form of a bipolar membrane.
  • the ion exchange membrane in the form of a bipolar membrane.
  • This has the particular advantage that the chemical conditions at the anode and the cathode of such an electrochemical reactor can be decoupled.
  • Such an electrochemical reactor also referred to below as a bipolar membrane reactor, makes it possible to carry out reactions in an alkaline medium on the one side, that is to say on the anode side or on the cathode side, and on the other side in an acid medium. It is thus possible to adapt the electrode reactions to those which are the most favorable for the reaction and, in particular, the costs of the membrane reactor. In particular, such an increased selectivity and a faster conversion rate of a desired reaction in a particular medium can be achieved.
  • the hydrogen evolution reaction at the cathode can be optimized by selecting an alkaline medium and ammonia formation on the anode side in an acidic medium.
  • a further advantage is an adapted choice of the catalysts, since different catalysts can be used for the same reaction in acidic and basic.
  • the medium can be freely selected on both sides by the bipolar membrane reactor so that significantly more cost-effective catalysts can be used if appropriate by adjusting the environment or character on the two sides of the ion exchange membrane.
  • Another advantage is in particular a reduction of operating costs of these bipolar membrane reactors.
  • the reduction potentials of the partial reactions at the electrodes are known to be strongly dependent on the particular environment.
  • the electrode potentials can be selected by appropriate choice of an acidic or basic environment on the respective side of the ion exchange membrane so that the lowest possible cell voltage can be adjusted in total.
  • a reduced cell voltage leads to a lower electrical consumption of the reactor and thus increases its economic operation.
  • a bipolar membrane as an ion exchange membrane, hydrogen can be efficiently generated at the cathode and urea can be decomposed highly efficiently at the anode into ammonia and C0 2 .
  • the bipolar membrane comprises an anion exchange membrane and a cation exchange membrane.
  • a bipolar membrane in particular makes it possible to separate different environments on both sides of the ion exchange membrane.
  • anions can be exchanged optimally by means of the anion exchange membrane and cations can be exchanged by means of the cation exchange membrane.
  • the anion exchange membrane and the cation exchange membrane are preferably separated from one another by a separating layer.
  • the separation layer contains a dissociation catalyst.
  • This is especially optimized for the splitting of water into protons (H + ) and hydroxide ions (OH).
  • the prevailing environment in the region of the anode and in the region of the cathode can be easily and reliably maintained by means of the dissociation catalyst.
  • the dissociation catalyst is or contains iron oxide.
  • it may be or contain iron (III) oxide (Fe 2 O 3 ).
  • the separating layer has a layer thickness in a range of about 500 nm to about 500 ⁇ m.
  • the anion exchange membrane carries an anodic catalyst layer on a side surface facing away from the cation exchange membrane.
  • the decomposition of urea can be favored in the desired manner.
  • anodic catalyst layer is arranged or formed between the anion exchange membrane and an anodic gas diffusion layer. Gases formed in the region of the anodic catalyst layer, in particular ammonia and carbon dioxide, can thus be diverted directly and safely directly through the anodic gas diffusion layer.
  • the anodic catalyst layer contains an anodic catalyst for oxidizing urea.
  • the anodic catalyst is nickel hydroxide (Ni (OH) 2 ) or contains nickel hydroxide.
  • the anodic catalyst layer contains at least one polymer which is also present in the anion exchange membrane.
  • the anodic catalyst layer has a pH greater than 7. In particular, it may have a pH of at least 9. Furthermore, it is favorable if the cation exchange membrane carries a cathodic catalyst layer on a side surface facing away from the anion exchange membrane.
  • the cathodic catalyst layer serves, in particular, to assist and optimize the hydrogen evolution reaction, ie the reduction of protons produced in the region of the separation layer by incorporation of electrons into molecular hydrogen.
  • the cathodic catalyst layer is arranged or formed between the cation exchange membrane and a cathodic gas diffusion layer. Due to the cathodic gas diffusion layer, the hydrogen can be safely and specifically removed.
  • the cathodic catalyst layer contains a cathodic catalyst for reducing protons (H + ).
  • H + protons
  • molecular hydrogen can be generated in a targeted manner.
  • the cathodic catalyst is or contains platinum (Pt), palladium (Pd), rhodium (Rh), osmium (Os), iridium (Ir) and / or ruthenium (Ru).
  • Pt platinum
  • Pd palladium
  • Rh rhodium
  • Os osmium
  • Ir iridium
  • Ru ruthenium
  • the cathodic catalyst layer contains at least one polymer, which is also contained in the cation exchange membrane.
  • the cathodic catalyst layer has a pH of less than 7, in particular a pH of less than 5.
  • the reduction of protons to molecular hydrogen preferably takes place in an acidic environment.
  • the anodic gas diffusion layer bears against an anodic bipolar plate and if the cathodic gas diffusion layer rests against a cathodic bipolar plate.
  • the bipolar plate can be formed with flow channels and form flow fields for the electrolysis products in order to be able to selectively divert them, ie ammonia and carbon dioxide on the one hand and hydrogen on the other hand.
  • the flow channels of the respective bipolar plates are preferably in fluid communication with the anodic gas diffusion layers so that the gases conducted through the gas diffusion layers can be diverted to and through the bipolar plates.
  • the electrochemical reactor comprises a membrane-electrode unit which comprises the bipolar membrane, the anodic catalyst layer, the cathodic catalyst layer, the anodic gas diffusion layer and the cathodic gas diffusion layer.
  • a membrane electrode assembly With such a membrane electrode assembly, an electrochemical reactor can be easily and inexpensively formed.
  • the membrane-electrode unit can be provided in particular as an independent unit with the named components. To form the electrochemical reactor, only two bipolar plates are needed, which must be brought into contact with the two gas diffusion layers of the membrane-electrode unit.
  • the electrochemical reactor comprises a catalytically coated membrane which comprises the bipolar membrane coated on the anode side with the anodic catalyst layer and on the cathode side with the cathodic catalyst layer.
  • a catalytically coated membrane can in particular be provided as a subcomponent of the electrochemical reactor.
  • Such a catalytically coated membrane can be used, in particular, to form a membrane-electrode unit if the catalytically coated membrane is contacted on both sides with a respective gas diffusion layer. This can be formed for example by a porous grid structure.
  • NEN gas diffusion layers by chemical or physical Be Schweizer- tungshabilit be applied to the respective catalyst layers.
  • the object stated in the introduction is also achieved in a method of the type described in the introduction according to the invention in that the ion exchange membrane is formed in the form of a bipolar membrane.
  • the bipolar membrane also referred to as a bipolar membrane
  • a bipolar membrane allows the chemical conditions at the anode and cathode of the electrochemical reactor to be decoupled.
  • different environments can be realized on the anode side or on the cathode side, for example alkaline or acidic environments, so that the respective electrode reactions can proceed optimally.
  • costs for the formation of a bipolar membrane reactor can be reduced in comparison to known membrane reactors or bipolar membranes.
  • a bipolar membrane which comprises an anion exchange membrane and a cation exchange membrane.
  • a bipolar membrane makes it possible, as described, to separate different environments on both sides of the ion exchange membrane from one another.
  • an optimal anion exchange can be achieved by means of the anion exchange membrane, an optimal cation exchange by means of the cation exchange membrane.
  • the anion exchange membrane and the cation exchange membrane are preferably separated from one another by a separating layer. It is advantageous if a dissociation catalyst is introduced into the separating layer. In particular, such a dissociation catalyst enables optimized splitting of water into protons (H + ) and hydroxide ions (OH). Both protons and hydroxide ions can be readily prepared if the release layer is kept moist.
  • a dissociation catalyst which is or contains iron oxide.
  • iron (III) oxide Fe 2 O 3
  • the dissociation catalyst can be used as the dissociation catalyst.
  • the release layer is formed with a layer thickness in a range of about 500 nm to about 500 pm.
  • an anodic catalyst layer is applied to a side surface of the anion exchange membrane facing away from the cation exchange membrane.
  • this can be applied by doctoring, dry spraying or wet spraying.
  • a coated bipolar membrane can thus be formed.
  • the anodic catalyst layer is disposed or formed between the anion exchange membrane and an anodic gas diffusion layer.
  • the gases which form in the region of the anodic catalyst layer that is to say in particular ammonia and carbon dioxide, can easily and safely be conducted away from the anodic catalyst layer through the anodic gas diffusion layer.
  • the anodic catalyst layer is formed with an anodic catalyst for oxidizing urea.
  • an anodic catalyst for oxidizing urea.
  • Such a catalyst promotes the decomposition of urea at the anode.
  • ammonia and carbon dioxide can be formed particularly efficiently at the anode.
  • an anodic catalyst is used or formed which is or contains nickel hydroxide (Ni (OH) 2 ).
  • an anodic catalyst layer which contains at least one polymer which is also present in the anion exchange membrane.
  • this procedure makes it possible to produce, for example, a chemical or mechanical bond between the anodic catalyst layer and the anion exchange membrane.
  • the polymer may form a support or framework structure of the anion exchange membrane carrying the anodic catalyst layer.
  • the anodic catalyst layer is formed with a pH greater than 7.
  • it can be formed with a pH greater than 9.
  • the urea decomposes particularly well.
  • a cathodic catalyst layer is formed on a side surface of the cation exchange membrane facing away from the anion exchange membrane.
  • a catalyst layer promotes the hydrogen evolution reaction and makes it possible to optimize it.
  • protons generated in the region of the separation layer are converted into molecular hydrogen by the absorption of electrons.
  • the electrochemical reactor can be produced in a simple manner if the cathodic catalyst layer is arranged or formed between the cation exchange membrane and a cathodic gas diffusion layer.
  • the cathodic gas diffusion layer may be provided as a porous support structure which is then brought into contact with the cathodic catalyst layer in a planar manner.
  • the cathodic gas diffusion Schicht also makes it possible to safely and selectively dissipate the molecular hydrogen produced in the region of the cathodic catalyst layer.
  • the cathodic catalyst layer is formed with a cathodic catalyst for reducing protons (H + ).
  • a cathodic catalyst allows a simple reduction of protons in the manner described to molecular hydrogen.
  • a cathodic catalyst comprising platinum (Pt), palladium (Pd), rhodium (Rh), osmium (Os), iridium (Ir) and / or ruthenium (Ru) is or contains.
  • a stable membrane unit can be formed if a cathodic catalyst layer is formed which contains at least one polymer which is also contained in the cation exchange membrane.
  • a polymer can form a stable scaffold both for the cation exchange membrane and for the cathodic catalyst layer and, moreover, also connect the latter mechanically and / or chemically.
  • the hydrogen evolution reaction at the cathode can be assisted when the cathodic catalyst layer having a pH less than 7 is formed.
  • it may be formed with a pH less than 5.
  • Such an acidic environment promotes the evolution of molecular hydrogen from protons.
  • the anodic gas diffusion layer is adjacent to an anodic bipolar plate and if the cathodic gas diffusion layer is formed adjacent to a cathodic bipolar plate.
  • the bipolar plates enable an optimal dissipation of the electrolysis products during operation of the electrochemical reactor.
  • ammonia on the one hand and hydrogen on the other can be separated from one another.
  • a membrane-electrode assembly which comprises the bipolar membrane, the anodic catalyst layer, the cathodic catalyst layer, the anodic gas diffusion layer and the cathodic gas diffusion layer.
  • a membrane electrode unit can be formed as an independent component of the electrochemical reactor.
  • an assembly of the electrochemical reactor can be simplified.
  • a catalytically coated membrane which comprises the bipolar membrane coated on the anode side with the anodic catalyst layer and on the cathode side with the cathodic catalyst layer.
  • a catalytically coated membrane can also form an independent building component for the formation of the electrochemical reactor.
  • the catalytically coated membrane is then provided on both sides with gas diffusion layers and bipolar plates, for example.
  • the object stated at the outset is achieved according to the invention in that the reducing agent generation device in the form of one of the electrochemical reactors described above Generating ammonia and hydrogen from a urea solution is formed by electrolysis.
  • an exhaust gas treatment system with an electrochemical reactor makes it possible in a simple and efficient manner to produce ammonia and hydrogen from a urea solution by electrolysis.
  • Both ammonia and hydrogen can be used to purify the exhaust gas to convert nitrogen oxides into molecular nitrogen and water.
  • the electrolysis of a urea solution in particular has the advantage that an exhaust gas treatment is possible even at low temperatures, unlike a thermal decomposition of urea, which preferably requires temperatures of more than 500 ° C.
  • the hydrogen produced can be used for the exhaust gas treatment.
  • the system comprises a first treatment chamber with a first exhaust gas inlet, a first exhaust gas outlet, a reducing agent inlet and a reduction catalytic converter, which first exhaust gas inlet can be connected directly or indirectly indirectly to a combustion device.
  • the hydrogen produced by the electrochemical reactor can be supplied to the first exhaust gas treatment chamber through the reducing agent inlet in order to reduce nitrogen oxides.
  • the system comprises an exhaust gas treatment agent store for storing the exhaust gas treatment agent.
  • the exhaust gas treatment agent can be provided in particular in the form of a urea solution from which, for example in a motor vehicle during operation, ammonia and hydrogen can be produced by electrolysis by means of the electrochemical reactor and used for exhaust gas treatment.
  • FIG. 1 shows a schematic representation of a structure of an embodiment of a membrane-electrode unit
  • FIG. 2 shows a schematic representation of a construction of an embodiment of an electrochemical reactor in the form of a bipolar membrane reactor
  • Figure 3 is a schematic representation of the membrane-electrode assembly of Figure 1 with the resulting reaction products
  • FIG. 4 shows a schematic representation similar to FIG. 3 with drawn reaction regions of the chemical reactions shown in FIG. 5;
  • FIG. 5 an exemplary representation of the electrochemical reactions in the regions I, II and III in FIG. 4;
  • FIG. 6 shows a schematic representation of the membrane-electrode unit from FIG. 3 with associated reaction equations for the use of the hydrogen developed at the cathode for nitrogen oxide reduction at low temperatures;
  • FIG. 7 shows a schematic representation of the membrane-electrode unit from FIG. 3, showing the electrochemical reaction equations for the reduction of nitrogen oxides at high temperatures using the ammonia formed at the anode;
  • Figure 8 a schematic representation of an embodiment of a
  • FIG. 9 shows a schematic representation of an embodiment of an electrochemical reactor which is arranged in an exhaust gas treatment agent store
  • FIG. 10 shows a schematic representation of a further exemplary embodiment of an exhaust gas treatment system
  • FIG. 11 reaction equations for nitrogen oxide removal by means of hydrogen.
  • FIG. 12 Reaction equations for removing nitric oxide by means of ammonia.
  • An embodiment of a membrane electrode assembly 10 comprises a bipolar membrane 12 having an anion exchange membrane 14 and a cation exchange membrane 16.
  • a separating layer 18 may be arranged or formed between the anion exchange membrane 14 and the cation exchange membrane 16, which preferably contains or consists of a dissociation catalyst 20.
  • the dissociation catalyst 20 may be iron oxide or dissociation catalyst 20 may include iron oxide.
  • iron (III) oxide Fe 2 O 3
  • the dissociation catalyst 20 may be iron oxide or dissociation catalyst 20 may include iron oxide.
  • iron (III) oxide Fe 2 O 3
  • the bipolar membrane 12 forms an ion exchange membrane 22.
  • the ion exchange membrane 22 can be used in particular as a finished product.
  • the bipolar membrane 12 may carry an anodic catalyst layer 24 and a cathodic catalyst layer 26.
  • the anion exchange membrane 22 carries the anodic catalyst layer 24 on a side surface 28 facing away from the cation exchange membrane 16.
  • the cation exchange membrane 16 carries the cathodic catalyst layer 26 on a side surface facing away from the anion exchange membrane 14.
  • the bipolar membrane 12 with the catalyst layers 24 and 26 forms a catalytically coated membrane 32, which can also be formed as a finished product, for example for producing an electrochemical reactor 34.
  • the membrane-electrode assembly 10 further comprises an anodic gas diffusion layer 36 and a cathodic gas diffusion layer 38 which are in contact with the anodic catalyst layer 24 on the one hand and with the cathodic catalyst layer 26 on the other hand such that the anodic catalyst layer 24 between the anodic gas diffusion layer 36 and the anion exchange membrane 14, and the cathodic catalyst layer 26 between the cation exchange membrane 16 and the cathodic gas diffusion layer 38.
  • the described membrane-electrode assembly 10 can be used to form the electrochemical reactor 35. It is arranged to form the same between two bipolar plates 40 and 42, so that the anodic bipolar plate 40 abuts the anodic gas diffusion layer 36 and the cathodic bipolar plate 42 at the cathodic gas diffusion layer 38th
  • the gas diffusion layers 36 and 38 are porous to discharge gaseous electrolysis products from the membrane-electrode assembly 10.
  • the bipolar plates 40 and 42 are provided with a plurality of flow channels 44 and 46, respectively, which form flow fields 48 and 50, respectively, for the gaseous electrolysis products.
  • the flow field 48 of the anodic bipolar plate 40 has a solution inlet 52, through which a solution containing the substance to be decomposed by electrolysis can flow into the flow channels 44 and come into contact with the anodic catalyst layer.
  • the anodic bipolar plate 40 also has an outlet 54 through which the gaseous electrolysis products formed at the anode can exit and be collected.
  • the cathodic bipolar plate 42 also has an outlet 56 for gaseous electrolysis products which form at the cathode.
  • the anodic bipolar plate 40 is electrically conductively connected to the positive pole of a voltage source 58, the cathodic bipolar plate 42 to the negative pole of the voltage source 58.
  • the separating layer 18 of the bipolar membrane 12 has a layer thickness 60 which may be in a range of about 0.1 ⁇ m to about 2 mm, in particular in a range of about 500 nm to about 500 ⁇ m.
  • Layer thicknesses 62 and 64 of the anodic catalyst layer 24 and the cathodic catalyst layer 26 are preferably in a range from about 100 pm to about 2 mm.
  • the electrochemical reactor 34 can be used in particular for producing ammonia 66 and hydrogen 68 from a urea solution 70.
  • the urea solution 70 contains 72 dissolved urea 74 in water.
  • the anodic catalyst layer 24 includes an anodic catalyst 76 for oxidizing urea 74.
  • the anodic catalyst 76 may be or contain nickel hydroxide (Ni (OH) 2 ).
  • the cathodic catalyst layer 26 includes a cathodic catalyst 78 for reducing protons (H + ).
  • the cathodic catalyst 78 may be or include platinum (Pt), palladium (Pd), rhodium (Rh), osmium (Os), iridium (Ir), and / or ruthenium (Ru).
  • anodic catalyst layer 24 may include one or more polymers that are also included in the anion exchange membrane 14 to form a stable mechanical composite.
  • the cathodic catalyst layer 26 may include one or more polymers that are also included in the cation exchange membrane 16.
  • the bipolar membrane 12 makes it possible to specify different acidic or alkaline environments on an anode formed by the anodic bipolar plate 40 and a cathode 82 formed by the cathodic bipolar plate 42.
  • an alkaline or basic medium is set at the anode with a pH Value greater than 7, in one embodiment with a pH of at least 9.
  • the alkaline / basic milieu prevails in particular on the anodic catalyst layer 24, which promotes the oxidation of the urea 74.
  • an acidic medium in the area of the cathode 82, in particular also the cathodic catalyst layer 26, can be set with a pH of less than 7.
  • the pH can be less than 5, whereby the hydrogen evolution reaction in the area of the cathodic catalyst layer 26 is improved.
  • the dissociation catalyst 20 in the separation layer 18 promotes the dissociation of water 72 into protons 84 (H + ) and hydroxide ions 86 (OH).
  • the protons 84 migrate in the electric field of the electrochemical reactor 34 toward the negatively charged cathode and form 88 molecular hydrogen 68 in the region of the cathodic catalyst layer with free electrons.
  • the urea solution 70 passes via the flow field 68 to the anodic catalyst layer 24. With release of electrons 88, the urea 74 dissociates into ammonia 66 and carbon dioxide 90.
  • Figure 5 shows the electrochemical reactions in the areas I, II and III, which are shown schematically in Figure 4.
  • water 72 dissociates to protons 84 and hydroxide ions 86.
  • nickel hydroxide Ni (OH) 2
  • Ni (OH) 2 nickel hydroxide
  • two partial reactions take place.
  • nickel hydroxide reacts with a Hydroxidion 86 to NiOOH, water 72 and a Electron (s).
  • urea 74 and water 72 are converted to carbon dioxide 90 and two molecules of ammonia 66.
  • protons 84 and electrons 88 are converted into molecular hydrogen 68.
  • FIG. 6 below shows by way of example the possible use of the hydrogen 68 formed at the cathode 82 for nitrogen oxide reduction at low temperatures.
  • partial equation (a) nitrogen monoxide is converted by the molecular hydrogen 68 to nitrogen and water 72.
  • partial equation (b) two molecules of nitrogen dioxide (NO 2 ) with two molecules of hydrogen 68 are converted into one molecule of nitrogen and two molecules of water 72.
  • Hydrogen 68 therefore enables effective exhaust gas purification of combustion exhaust gases even at low temperatures by reducing the nitrogen oxides contained therein to molecular nitrogen.
  • Nitrogen oxides can also be converted into molecular nitrogen and water 72 with the ammonia 66 produced with the electrochemical reactor 34.
  • the ammonia produced at the anode 80 of the electrochemical reactor 34 can be used in accordance with equation (a) in FIG. 7 for the reduction of nitrogen monoxide NO to molecular nitrogen N 2 .
  • Equation (b) in FIG. 7 describes the reaction of nitrogen dioxide NO 2 with ammonia 66 to give molecular nitrogen N 2 and water 72.
  • an electrochemical reactor 34 can be used, for example, in a system 92 for the exhaust gas treatment of a combustion device 94, for example in the form of a motor 96.
  • the electrochemical reactor 34 may be disposed in an exhaust treatment agent reservoir 98 that includes an exhaust treatment agent 100 in the form of the urea solution 70.
  • Hydrogen 68 produced by electrolysis is passed from the cathode 82 to a first treatment chamber 102, in which a Reduktionskata- is lysator for a selective catalytic reduction of nitrogen oxides already at low temperatures by means of hydrogen 68 is included.
  • Exhaust 104 emitted by the engine 96 is supplied to the first treatment chamber 102 for exhaust treatment.
  • Exhaust gas 106 purified in a first stage is fed to a second treatment chamber 108 in which another catalyst is disposed to assist in the selective catalytic reduction of nitrogen oxides by means of ammonia 66.
  • Ammonia 66 is supplied to the second treatment chamber 108 with the carbon dioxide 90, which is likewise formed during the electrolysis in the electrochemical reactor 34, in which the prepurified exhaust gas 106 is cleaned at high temperatures in a second purification stage of nitrogen oxides still remaining in the exhaust gas 106.
  • the second treatment chamber 108 leaves completely purified exhaust gas 110, which no longer contains any nitrogen oxides, but only the reaction products of the reaction equations indicated in FIGS. 6 and 7, ie molecular nitrogens and water. Furthermore, further combustion products can be contained in the exhaust gas 110, such as, for example, carbon dioxide 90, which is also supplied by the electrochemical reactor 34 to the second treatment chamber 108 as an inert gas and emitted by the latter into the exhaust gas 110.
  • FIG. 9 schematically shows a reducing agent generating device 112 in the form of an electrochemical reactor 34, which is designed as a urea electrolyzer. With this reducing agent generating device 112, reducing agents 114 and 116 can be produced, namely in the form of ammonia 66 and molecular hydrogen 68.
  • the electrochemical reactor 34 is fluidly connected to the Abgas accompaniments- means memory 98. This is realized, as illustrated by way of example in FIG. 2, in that the electrochemical reactor 34 is arranged in the exhaust gas treatment agent reservoir 98, which is designed as a tank 118 containing urea solution 70.
  • the electrochemical reactor 34 is designed in the form of a chamber-separated ammonia electrolyzer for separating the hydrogen 68 formed during the electrolysis from the resulting ammonia 66.
  • a urea solution 70 is contained as exhaust gas treatment agent 100.
  • the electrochemical reactor comprises a closed cathode chamber 120 to receive the hydrogen 68 produced at the cathode 82 to keep it separate from the ammonia 66.
  • the ammonia electrolyzer may in particular comprise a plurality of cathode chambers 120.
  • the ammonia electrolyzer further comprises an open anode chamber 50 so that the ammonia 66 and carbon dioxide 90 formed in the electrolysis can be collected and stored in the tank 118.
  • the cathode chambers 120 are fluidly connected to each other and led to a common hydrogen outlet 122. Further, an outlet 124 is disposed or formed on the tank 118 to discharge the gaseous mixture of ammonia 66 and carbon dioxide 90 that collects above the urea solution 70 from the tank 118.
  • the hydrogen outlet 122 of the exhaust gas treatment agent reservoir 98 shown by way of example in FIG. 9 can in particular be connected directly or indirectly to an exhaust gas line which directs the exhaust gas 104 into the first treatment chamber 102.
  • the hydrogen outlet 122 may also be connected directly to the first treatment chamber 102 to direct reducing agent in the form of hydrogen 68 into the first treatment chamber 102.
  • the outlet 124 may also be in fluid communication with the second treatment chamber 108 for supplying the ammonia 66 thereto, as described above in connection with FIG. 8, for reducing nitrogen oxides remaining in the exhaust gas 106.
  • FIG. 10 shows by way of example a system 92 in the form of an exhaust gas purification system 126 for an internal combustion engine 96 in the form of a diesel engine 128.
  • the exhaust gas 104 resulting from combustion in the diesel engine 128 may optionally be directed into a diesel oxidation catalyst 130.
  • oxygen can be introduced in a manner not shown in order to further oxidize the combustion gases.
  • an oxidation catalyst 132 may be disposed in the diesel oxidation catalyst 130.
  • the partially oxidized exhaust gas 104 is directed to a diesel particulate filter 134.
  • the exhaust gas 104 is conducted into the first treatment chamber 102.
  • a nitrogen oxide content is measured with a measuring device 136.
  • This measuring device 136 can be designed in particular in the form of a nitrogen oxide sensor.
  • the measuring device 136 is connected to a control and / or regulating device 138 via a connecting line 140 in order to transmit the measured nitrogen oxide values to the control and / or regulating device 138.
  • the first treatment chamber 102 is further supplied with molecular hydrogen 68 and introduced through a hydrogen inlet 142.
  • a temperature measuring device 144 for measuring a temperature in the first treatment chamber 102 may be arranged or formed on the first treatment chamber 102.
  • the temperature measuring device 144 may be designed in particular in the form of a temperature sensor.
  • the temperature measuring device 144 is connected to the control and / or regulating device 138 in a control-effective manner via a control or connecting line 146.
  • the exhaust gas 106 is introduced from the first treatment chamber 102 into the second treatment chamber 108, in which a reduction catalyst is arranged.
  • the exhaust gas 106 is supplied to ammonia 66 via an inlet 148 before entering the second treatment chamber 108.
  • the exhaust gas 110 after exiting the second treatment chamber 108, can be measured at a further measuring device 150 for measuring a nitrogen oxide content of the exhaust gas 110 be led past.
  • the measuring device 150 for example in shape a nitrogen oxide sensor, is connected to the control and / or regulating device 138 with control effect via a further connecting line 152.
  • Exhaust 110 exiting the second treatment chamber 108 is optionally directed through a muffler chamber 154 and ultimately to a tail tube 156 from which the exhaust gases 110 exit. These are nitric oxide-free with optimum adjustment of the system 92.
  • the amount of ammonia 66 and hydrogen 68 produced by electrolysis with the electrochemical reactor 34 can be specifically controlled and / or regulated with the control and / or regulating device 138. This makes it possible in particular to treat the exhaust gases 104 even during a cold start of the internal combustion engine 96 in such a way that the otherwise usual cold-start pollutants are not contained in the exhaust gas 110.
  • FIG. 6 shows by way of example the six reaction equations of a selective catalytic reduction using hydrogen.
  • molecular oxygen can additionally be fed in order to promote an oxidation of nitrogen monoxide NO to nitrogen dioxide NO 2 .
  • complete conversion of nitrogen dioxide with hydrogen to nitrogen and water can be achieved according to the following equation:
  • FIG. 12 shows by way of example three reaction equations of a selective catalytic reduction of nitrogen oxides using ammonia.
  • Equation (a) forms the so-called “standard SCR equation”.
  • SCR selective catalytic reduction
  • Equation (b) in Figure 12 represents the so-called “Fast SCR Equation.” According to this equation, a mixture of nitrogen monoxide and nitrogen dioxide can be converted to molecular nitrogen and water using ammonia.
  • Equation (c) represents the so-called “slow SCR equation.” According to this reaction equation, nitrogen dioxide can be converted to molecular nitrogen and water in conjunction with ammonia.
  • the described embodiments of electrochemical reactors for generating ammonia and hydrogen from a urea solution by electrolysis can be used as described for the exhaust gas purification of combustion devices 94. They represent an efficient way of purifying exhaust gas from combustion devices 94 of nitrogen oxides already at the start of the same, that is to say in particular at even low combustion temperatures.

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Abstract

L'invention vise à améliorer un réacteur électrochimique destiné à produire de l'ammoniac et de l'hydrogène à partir d'une solution d'urée par électrolyse, lequel réacteur électrochimique comprend une anode et une cathode séparées l'une de l'autre par une membrane échangeuse d'ions, de sorte que les produits souhaités puissent être produits simplement et de manière sûre. À cet effet, la membrane échangeuse d'ions se présente sous la forme d'une membrane bipolaire. L'invention concerne en outre un procédé amélioré destiné à produire de l'ammoniac et de l'hydrogène à partir d'une solution d'urée par électrolyse, ainsi qu'un système amélioré destiné au traitement des gaz d'échappement de dispositifs de combustion, en particulier de moteurs à combustion.
PCT/EP2019/061996 2018-05-11 2019-05-10 Réacteur électrochimique et procédé de production d'ammoniac et d'hydrogène à partir d'une solution d'urée par électrolyse WO2019215309A1 (fr)

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CN115305477A (zh) * 2022-07-01 2022-11-08 中国华能集团清洁能源技术研究院有限公司 电解尿素-二氧化碳还原制取合成气的系统和方法

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DE102020120702A1 (de) 2020-08-05 2022-02-10 Friedrich Boysen GmbH & Co KG. Verfahren zur Herstellung eines Nanopartikelmaterials und Nanopartikelmaterial

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CN115094454A (zh) * 2022-07-01 2022-09-23 中国华能集团清洁能源技术研究院有限公司 用于尿素电解制氢和碳还原的电解池及方法
CN115305477A (zh) * 2022-07-01 2022-11-08 中国华能集团清洁能源技术研究院有限公司 电解尿素-二氧化碳还原制取合成气的系统和方法
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