WO2019206392A1 - Procédé de décokéfaction d'une anode d'un dispositif à pile à combustible - Google Patents

Procédé de décokéfaction d'une anode d'un dispositif à pile à combustible Download PDF

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Publication number
WO2019206392A1
WO2019206392A1 PCT/EP2018/060282 EP2018060282W WO2019206392A1 WO 2019206392 A1 WO2019206392 A1 WO 2019206392A1 EP 2018060282 W EP2018060282 W EP 2018060282W WO 2019206392 A1 WO2019206392 A1 WO 2019206392A1
Authority
WO
WIPO (PCT)
Prior art keywords
anode
oxygen
cathode
fuel cell
cell device
Prior art date
Application number
PCT/EP2018/060282
Other languages
German (de)
English (en)
Inventor
Ralf Brandenburger
Maxime Carre
Original Assignee
Robert Bosch Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Priority to PCT/EP2018/060282 priority Critical patent/WO2019206392A1/fr
Publication of WO2019206392A1 publication Critical patent/WO2019206392A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a method for removing Kohlenstoffablage ments at an anode of a fuel cell unit, which has the anode, a cathode and an arranged between the anode and the cathode electrolyte.
  • a DC electrical voltage between the cathode and the anode is applied and the anode is supplied with an oxygen-containing gas, wherein at least a portion of the oxygen is provided to connect with carbon deposits on the anode to form gaseous carbon monoxide ,
  • a “fuel cell unit” is to be understood in this context, in particular a unit with at least one fuel cell, which is vorgese hen, at least one chemical reaction energy at least one, in particular continuously supplied, fuel gas, in particular hydrogen and / or carbon monoxide, and at least one cathode gas , In particular oxygen, in particular special convert into electrical energy.
  • the at least one fuel cell is preferably designed as a solid oxide fuel cell (SOFC).
  • SOFC solid oxide fuel cell
  • the at least one fuel cell unit comprises a plurality of fuel cells, which are arranged in particular in a fuel cell stack.
  • “Provided” is to be understood in particular to be specially programmed, designed and / or equipped. the.
  • the fact that an object is intended for a specific function should be understood in particular to mean that the object fulfills and / or executes this specific function in at least one application and / or operating state.
  • the Ano de the fuel cell unit is formed at least substantially of nickel.
  • the cathode of the fuel cell unit has in particular a perovskite structure.
  • the anode and the cathode are gas-tightly separated from one another by the electrolyte, at least in essence.
  • the anode and the cathode each have an open-porous structure. Only for the transport of electric charge neces-ended oxygen anions can pass through the electrolyte material.
  • the conductivity of the ceramic electrolyte depends in particular on the composition of the material, on the design boundary conditions and / or on the operating temperature.
  • carbonaceous fluid fuels such as natural gas with the main constituent CH 4
  • carbon deposits can form along the anode filament and in particular directly at the anode
  • the anode is supplied in one process step, an oxygen-containing gas, preferably air.
  • an oxygen-containing gas preferably air.
  • Existing carbon deposits on the anode react with the oxygen molecules of the oxygen-containing gas to form gaseous carbon monoxide.
  • a DC electrical voltage between the cathode and the anode is applied by means of a DC voltage source.
  • a negative electrical potential is applied to the anode and a positive electrical potential is applied to the cathode.
  • a generic method can be provided with advantageous properties with respect to a removal of carbon deposits from the anode.
  • a removal of Kohlenstoffab deposits of the anode advantageously without dismantling work and / or BeCdi conditions of the anode done.
  • carbon deposits on the anode can advantageously be easily and / or reliably removed by supplying an oxygen-containing gas.
  • an electrical DC voltage between the anode and the cathode can be advantageously prevented who the that is formed by excess oxygen nickel oxide on the anode.
  • part of the oxygen diffuses into the anode, the oxygen molecules being split and By supplying electrons oxygen anions are formed.
  • a portion of the oxygen that has not combined with the carbon deposits to gaseous carbon monoxide flows into the porous structure of the anode.
  • the oxygen molecules diffused into the anode are split into oxygen atoms.
  • the oxygen atoms take up electrons supplied to the anode, forming oxygen anions.
  • damage to the anode by the formation of nickel oxide can be advantageously avoided.
  • the oxygen anions flow through the electrolyte into the cathode in at least one method step on account of the driving force of the direct electrical voltage.
  • the electrolyte has a bidirectional permeability for oxygen anions.
  • the oxygen anions flow from the anode towards the cathode through the electrolyte. After passing through the electrolyte, the oxygen anions flow into the cathode.
  • the part of the oxygen which has not been combined with the carbon deposits to form gaseous carbon monoxide can advantageously be transported in the form of oxygen anions from the anode to the cathode.
  • the oxygen molecules in at least one process step out of the cathode.
  • the electrons given off by the oxygen anions flow to a positive pole of the DC voltage which is applied between the anode and the cathode.
  • the positive pole of the track voltage is connected to the Katho de.
  • the oxygen atoms formed by the emission of the electrons bind to oxygen molecules.
  • the oxygen molecules flow out of the porous cathode.
  • the invention is based on a fuel cell device, which is intended to be equipped with a hydrocarbon-containing fluid fuel. to be powered with a fuel cell unit having an anode, a cathode and an electrolyte disposed between the anode and the cathode.
  • the fuel cell device has an oxygen supply, which is provided to supply an oxygen-containing gas to the anode to remove carbon deposits on the anode.
  • the oxygen supply is provided to the anode during a cleaning operation state an oxygen-containing gas, in particular air supply.
  • the oxygen supply unit has, in particular, a fluid line which opens into an anode circuit of the fuel cells.
  • the oxygen supply unit in particular has a compressor for conveying the oxygen-containing gas.
  • the oxygen supply has at least one valve, which is provided to separate the oxygen supply during a normal operation of the fuel cell device fluid technically from the anode circuit of the fuel cell device.
  • removal of carbon deposits from the anode can advantageously be carried out without deinstallation work and / or damage to the anode.
  • carbon deposits on the anode can advantageously be easily and / or reliably removed by supplying an oxygen-containing gas.
  • a "fuel cell device” is to be understood as meaning, in particular, a device for stationary and / or mobile extraction of, in particular, electrical and / or thermal energy using at least one fuel cell unit.
  • the hydrocarbon-containing fluid fuel is preferably a natural gas.
  • a "natural gas” is to be understood as meaning in particular a gas and / or a gas mixture, in particular a natural gas mixture, which preferably comprises at least one alkane, in particular methane, ethane, propane and / or butane.
  • the natural gas may have further constituents, such as in particular carbon dioxide and / or nitrogen and / or oxygen and / or sulfur compounds.
  • a "reformer unit” is to be understood as meaning, in particular, a chemical-technical unit for at least treating at least the hydrocarbonaceous fluid, in particular the natural gas, in particular by steam reforming, by partial oxidation, by autothermal reforming and / or by a Combination of a steam reforming with a C0 2 dry reforming, in particular for obtaining a Fuel gas, in particular hydrogen, and / or for breaking higher-chain Alka ne understood ne.
  • a “desulfurization unit” is to be understood in this context in particular a unit which is intended, preferably by at least one physical and / or chemical adsorption and / or absorption method, a volume and / or molar content of sulfur compounds in the natural gas in particular below a predetermined limit value and preferably at least substantially to remove ent from the natural gas.
  • the fuel cell device has at least one DC voltage source, which is provided for removing carbon deposits on the anode to produce a DC voltage between the anode and the cathode.
  • the DC voltage source is provided to apply a negative electrical potential to the anode and to apply a positive electrical potential to the cathode.
  • inventive method and / or the fuel cell device according to the invention should / should not be limited to the above-described application and Ausrete tion form.
  • the method according to the invention and / or the fuel cell device according to the invention can have a number of individual elements, components and units and / or method steps deviating from a number of individual elements, components and units mentioned herein for fulfilling a function described herein.
  • Fig. 1 is a schematic representation of a fuel cell device with a fuel cell unit, an anode gas processor and a Brennerein unit and
  • FIG. 2 is a flowchart of a method for removing carbon deposits at the anode of the fuel cell unit.
  • FIG. 1 shows a schematic representation of a fuel cell device 38 with a fuel cell unit 14.
  • the fuel cell device 38 is intended to be operated with a fluidic hydrocarbon-containing fuel 40, for example natural gas.
  • the fuel cell unit 14 is provided for generating electric power.
  • the fuel cell unit 14 is shown here in simplified form as a fuel cell 46. However, it is useful
  • the fuel cell unit 14 has an anode 12 and a cathode 16.
  • the anode 12 is during a normal operation of the
  • Fuel cell unit 14 a recovered from the fuel 40 fuel gas 48, in particular hydrogen, fed.
  • the anode 12 is at least a large part of nickel.
  • the cathode 16 is during normal operation of the
  • Fuel cell unit 14 an oxygen-containing gas 22, in particular air, supplied.
  • the anode 12 and the cathode 16 each have a porous structure.
  • Des Weite ren the fuel cell device 38 to an inverter 52, which is intended to transform the electrical energy generated by the fuel cell unit 14 for feeding into an electrical network 54.
  • the fuel cell device 38 has a desulfurization unit 56 upstream of the fuel cell unit 14.
  • Desulfurization unit 56 is provided to at least partially desulfurize fuel 40. For recovering the fuel gas 48, the
  • Fuel cell device 38 one of the desulfurization 56th
  • the fuel 40 is fed into the fuel cell device 38 via a supply line 60 during operation of the fuel cell unit 14.
  • Fuel 40 is conveyed by means of a compressor 62.
  • the emerging from the reformer unit 58 fuel gas 48 is the anode 12 of the fuel cell unit 14 leads supplied.
  • the oxygen-containing gas 22 is fed via a further supply line 64 into the fuel cell device 38.
  • the oxygen-containing gas 22 is conveyed by means of a compressor 66.
  • Fuel cell unit 14 the oxygen-containing gas 22 by means of a
  • Heat exchanger 68 is heated.
  • the fuel cell device 38 has an afterburner 70.
  • the afterburner 70 is connected downstream of the fuel cell unit 14 in terms of flow.
  • the afterburner 70 is a part of an anode exhaust gas 72 of
  • Fuel cell unit 14 is supplied.
  • the afterburner 70 is intended to combust combustible materials remaining in the anode exhaust gas 72 of the fuel cell unit 14, in particular unreacted hydrogen.
  • An oxygen required for operation of the afterburner 70 is supplied to the afterburner 70 in the form of a cathode exhaust gas 74 of the fuel cell unit 14.
  • An exhaust gas 76 of the afterburner 70 is discharged from the fuel cell device 38.
  • Fuel cell device 38 also has a recirculation circuit 78, which is provided for a partial recirculation of the hydrogen and water-containing anode exhaust gas 72 of the fuel cell unit 14.
  • the recirculation circuit 78 is provided, in particular, for the anode exhaust gas 72 of the fuel cell unit 14 at least partially for mixing with the desulphurised fuel 90
  • a compressor 80 is arranged.
  • the fuel cell device 38 has a starting burner 82.
  • desulfurized fuel 90 and oxygen-containing gas 22 are supplied to the starting burner 82, which is provided to heat the oxygen-containing gas 22 during startup.
  • the heated oxygen-containing gas 22 is the
  • FIG. 2 shows the fuel cell unit 14 in a simplified schematic representation during a cleaning operation of the fuel cell device 38.
  • a method for removing carbon deposits 10 at the anode 12 of the fuel cell unit 14 comprising the anode 12, the cathode 16, and a between the anode 12 and the cathode 16 arranged electrolyte 18, executed.
  • the electrolyte 18 has an anion conductivity for conducting oxygen anions 36.
  • a DC electrical voltage 20 between the cathode 16 and the anode 12 is attached and the anode 12, an oxygen-containing gas 22 is supplied, wherein at least a portion of the oxygen 24 is provided, with carbon deposits 10 at the anode 12th to connect to gaseous carbon monoxide 26.
  • the gaseous carbon monoxide 26 is discharged from the anode 12.
  • the cathode gas 16 is supplied to the oxygen-containing gas 22.
  • the fuel cell device 38 has an oxygen supply 42, which is provided to supply an oxygen-containing gas 22 to the anode 12 for removing carbon deposits 10 at the anode 12.
  • the oxygen supply 42 may be diverted from the supply line 64 as shown in FIG.
  • the oxygen supply 42 may be formed as a separate supply.
  • the oxygen supply 42 has a valve 86, which is provided to close the oxygen supply 42 in a normal operation of the fuel cell device 38 relative to the anode 12.
  • the fuel cell device 38 has a DC voltage source 44, which is provided to generate a DC voltage 20 between the anode 12 and the cathode 16 for removing carbon deposits 10 on the anode 12.
  • the DC voltage source 44 may for example be gebil det of the inverter 52, which is operated in the cleaning operation as a rectifier.
  • the DC voltage source 44 is provided to put on the anode 12, a negative electrical cal potential 28 and at the cathode 16, a positive electrical potential 30 to.
  • the Sauerstoffmo molecules 32 are cleaved to oxygen atoms 88. Take the oxygen atoms 88 through the DC voltage source 44 of the anode 12 supplied to electrons 34, whereby oxygen anions 36 are formed.
  • the oxygen anions 36 flow due to the driving force of the DC electrical voltage 20 to the electrolyte 18, flow through this and flow into the cathode 16 a.
  • the electrons 34 are separated from the oxygen anions 36.
  • the oxygen atoms 88 thus formed combine to form oxygen molecules 32.
  • the oxygen molecules 32 flow out of the cathode 16 and are conducted away from it.

Abstract

La présente invention concerne un procédé pour supprimer des dépôts de carbone (10) sur une anode (12) d'une unité de pile à combustible (14) qui comprend l'anode (12), une cathode (16) et un électrolyte (18) disposé entre l'anode (12) et la cathode (16). Selon la présente invention, au cours d'au moins une étape de procédé, une tension électrique continue (20) est appliquée entre la cathode (16) et l'anode (12), et un gaz oxygénifère (22) est apporté à l'anode (12), une partie de l'oxygène (24) étant destinée à se combiner avec les dépôts de carbone (10), sur l'anode (12) pour former un monoxyde de carbone gazeux (26).
PCT/EP2018/060282 2018-04-23 2018-04-23 Procédé de décokéfaction d'une anode d'un dispositif à pile à combustible WO2019206392A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2018/060282 WO2019206392A1 (fr) 2018-04-23 2018-04-23 Procédé de décokéfaction d'une anode d'un dispositif à pile à combustible

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2018/060282 WO2019206392A1 (fr) 2018-04-23 2018-04-23 Procédé de décokéfaction d'une anode d'un dispositif à pile à combustible

Publications (1)

Publication Number Publication Date
WO2019206392A1 true WO2019206392A1 (fr) 2019-10-31

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010044043A1 (en) * 2000-05-18 2001-11-22 Badding Michael E. Solid oxide fuel cells with symmetric composite electrodes
US20090110993A1 (en) * 2007-10-30 2009-04-30 Monika Backhaus-Ricoult Segmented solid oxide fuel cell stack and methods for operation and use thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010044043A1 (en) * 2000-05-18 2001-11-22 Badding Michael E. Solid oxide fuel cells with symmetric composite electrodes
US20090110993A1 (en) * 2007-10-30 2009-04-30 Monika Backhaus-Ricoult Segmented solid oxide fuel cell stack and methods for operation and use thereof

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