WO2016041654A1 - Dispositif de piles à combustible comprenant un dispositif de traitement de gaz anodique amélioré - Google Patents

Dispositif de piles à combustible comprenant un dispositif de traitement de gaz anodique amélioré Download PDF

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Publication number
WO2016041654A1
WO2016041654A1 PCT/EP2015/065936 EP2015065936W WO2016041654A1 WO 2016041654 A1 WO2016041654 A1 WO 2016041654A1 EP 2015065936 W EP2015065936 W EP 2015065936W WO 2016041654 A1 WO2016041654 A1 WO 2016041654A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel cell
cell device
operating
anode
oxygen
Prior art date
Application number
PCT/EP2015/065936
Other languages
German (de)
English (en)
Inventor
Timo Bosch
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
Publication of WO2016041654A1 publication Critical patent/WO2016041654A1/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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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 fuel cell device and a method for operating a fuel cell device having at least one fuel cell unit and at least one anode exhaust gas recirculation.
  • DE1393804A1 discloses a catalyst and a process for the autothermal, catalytic steam reforming of hydrocarbons using the catalyst. Disclosure of the invention
  • the fuel cell device according to the invention with the features of the main claim is characterized by at least one anode gas processor, which is intended to perform various reforms during different operating phases.
  • a supplied fuel such as natural gas or a supplied fuel-air mixture can be flexibly reformed depending on the operation of the fuel cell device.
  • the various reforms such as e.g. Reforming by partial oxidation and steam reforming, both temporally separated, and performed in parallel with each other in time.
  • the fuel cell device according to the invention can be operated particularly efficiently.
  • the at least one anode gas processor is fluidically ahead of the minimum switched at least one fuel cell unit.
  • a reformate resulting from the various reforms can be fed directly to the fuel cell unit.
  • at least one oxygen supply is arranged in terms of flow in front of the at least one anode gas processor.
  • the oxygen-carbon ratio (O / C) of the fuel-air mixture supplied to the anode gas processor can be adapted for a desired reforming.
  • the at least one anode gas processor comprises a catalyst material. Due to the possibility of carrying out various reforms by means of a catalyst material, it is not necessary to install complex, multipartite reformer systems.
  • the catalyst material comprises at least one noble metal, in particular platinum and / or rhodium.
  • the invention also relates to a method for operating a fuel cell device.
  • the method is characterized in that by means of at least one anode gas processor various reforms during different operating phases are performed.
  • various reforms for a flexible and efficient operation of the fuel cell device can be specifically used.
  • the anode gas processor in particular the catalyst material, is heated before being reformed, preferably locally.
  • the anode gas processor is heated before being reformed, preferably locally.
  • only one component needs to be heated for efficient reforming, which in turn saves energy.
  • oxygen is supplied to the anode side of the at least one anode gas processor.
  • oxygen is supplied on the anode side during the first operating phase.
  • a reforming by partial oxidation is possible and can also be influenced by the amount of oxygen supplied.
  • reforming is carried out by partial oxidation and steam reforming. This allows a steady transition to normal operation.
  • the partial oxidation in the transition phase can be selectively controlled or reduced.
  • the fuel cell unit can be supplied with the required amount of reformate, preferably hydrogen, for normal operation.
  • reformate preferably hydrogen
  • Oxygen supplied whereby a partial oxidation reforming during normal operation is avoided.
  • At least one further reformate is cooled by means of at least one further oxygen supply.
  • Fig. 1 is a schematic representation of an embodiment of the fuel cell device according to the invention.
  • Fig. 2 is a schematic representation of another embodiment of the fuel cell device according to the invention.
  • the embodiments of the fuel cell device 10 according to the invention are shown substantially only on the anode side, since in the following mainly anode-side processes are described.
  • Fig. 1 shows a schematic representation of an embodiment of the fuel cell device 10 according to the invention with a fuel cell unit 12 and an anode exhaust gas recirculation 14.
  • the fuel cell device 10 is characterized by an anode gas processor 16, which is intended to perform various reforms during different operating phases.
  • anode gas processor 16 which is intended to perform various reforms during different operating phases.
  • a fuel or a fuel-air mixture can be processed by a specific reforming, in the exemplary embodiment by partial oxidation reforming and / or by steam reforming.
  • the various reforms differ from one another and, depending on the operating phase of the fuel cell device 10, can be carried out both temporally separate from each other, as well as temporally parallel to each other.
  • the fuel cell unit 12 includes a fuel cell 13 having an anode 15, a cathode 17, and an electrolyte 19 interposed therebetween.
  • the fuel cell unit 12 includes an SOFC fuel cell 13.
  • the fuel cell unit 12 a fuel cell stack, that is, a plurality of
  • Fuel cells 13 includes.
  • natural gas is supplied as fuel by means of a fuel supply 18, which is a component of the fuel cell device 10.
  • a fuel supply 18 which is a component of the fuel cell device 10.
  • the fuel or natural gas is the
  • Anodengasskeor 16 can be fed.
  • the anode gas processor 16 is fluidically connected in front of the at least one fuel cell unit 12.
  • an oxygen supply 22 is arranged in terms of flow in front of the at least one anode gas processor 16, through which air or oxygen can be added to the supplied fuel.
  • the oxygen supply 22 is arranged so that oxygen is supplied directly to the anode gas processor 16.
  • the supply of fuel or natural gas is controlled by a valve 24, while the air or oxygen supply is controlled by a further valve 26 Alternatively, it is also conceivable that the supply of fuel or natural gas and / or air or Oxygen is regulated by blower.
  • the anode gas processor 16 includes a catalyst material 28 through which various reforms can be performed.
  • the anode gas processor 16 consists of a reaction chamber 30, which contains the catalyst material 28.
  • the catalyst material 28 comprises at least one noble metal. In the exemplary embodiment shown, these are platinum and rhodium.
  • the catalyst material 28 is made of alternating, in the flow direction, honeycomb Layers constructed, each comprising platinum and rhodium. It is introduced into the anode gas processor 16 so as to completely fill the reaction chamber 30. Due to the honeycomb structure of the catalyst material 28, the supplied fuel can pass through the anode gas processor 16 so that it always comes into contact with the catalyst material 28 and thus a corresponding reforming of the fuel is performed.
  • the catalyst material 28 has a planar layer structure and is mounted in the anode gas processor on the inner wall of the reaction chamber.
  • the fuel or the fuel-air mixture can then coaxially enclosed by the catalyst material 28, the anode gas processor 16 and the reaction chamber 30 to flow through.
  • the fuel cell device 10 according to the invention is operated in such a way that different reforms are carried out during different operating phases by means of the anode gas processor 16, thereby enabling flexible operation of the fuel cell device 10.
  • Prior to commissioning of the fuel cell device 10 according to the invention is predominantly air or oxygen in the anode-side lines of the fuel cell device 10.
  • This oxygen is particularly harmful for the fuel cell unit 12, since it leads to an oxidation of these components.
  • this oxygen can be rendered harmless in a desired reforming, for example by partial oxidation.
  • the anode gas processor 16 or the catalyst material 28 is heated before being reformed.
  • the anode gas processor 16 or the catalyst material 28 is locally heated. This is about a heating wire 31 accomplished, which is in contact with the catalyst material.
  • the fuel cell device 10 is supplied with fuel via the fuel supply 18.
  • oxygen is supplied on the anode side upstream of the at least one anode gas processor 16.
  • valves 24, 26 we set the ratio between the supplied oxygen or the air and the fuel or natural gas.
  • the fuel-air mixture is conveyed by the pump 20 to the anode gas processor 16. There is a partial phase oxidation carried out during a first phase of operation or during the start-up phase.
  • CPOX Catalytic Partial Oxidation
  • the hydrocarbons contained in the fuel are oxidized at the catalyst 28 with oxygen and thus substantially to Carbon monoxide and hydrogen reformed.
  • the catalyst material 28 By the catalyst material 28, the required reforming temperature is lowered.
  • the reforming reaction is exothermic, resulting in the further course of the reforming process in the anode gas processor 16 temperatures of about 800 ° C to 1200 ° C arise.
  • oxygen-carbon ratio (O / C) of the anode gas processor 16 supplied fuel-air mixture is controlled so that after the reforming by partial oxidation no oxygen remains.
  • the oxygen-carbon ratio (O / C) during the start-up phase is regulated to a value of approximately 1.2. This ensures that there are no significant carbon deposits.
  • the oxygen-carbon ratio is controlled by a ⁇ -control.
  • the air or oxygen which is present on the anode side in the lines of the fuel cell device 10 prior to startup of the fuel cell device 10, used for the partial oxidation and thus also rendered harmless for the components of the fuel cell unit 12.
  • the recovered reformate flows through a heat exchanger 32. Subsequently, the reformate is supplied to the fuel cell unit 12 on the anode side, the fuel cell unit 12 being warmed up by the high temperature of the reformate.
  • the reformate After leaving the fuel cell unit 12, the reformate is recycled via the anode exhaust gas recirculation 14 to the downstream materials of the pump 20 and the anode exhaust gas processor 16.
  • the heat exchanger 32 Through the heat exchanger 32, a heat balance between the reformate, which leaves the fuel cell unit 12, and the reformate, which is supplied to the fuel cell unit.
  • the material flow which is supplied to the anode gas processor 16, preheated.
  • the hydrogen contained in the reformate is electrochemically reacted to generate electricity and heat and it is in a second phase of operation, a transition phase, a partial oxidation and a steam reforming performed. Since a steam formation proceeds endothermic, while a partial oxidation is exothermic prevails in this transition phase compared to the start-phase lowered on average temperature.
  • the fuel cell unit 12 is simultaneously supplied via an air supply line 34 on the cathode side air or oxygen.
  • exhaust gas is produced which essentially contains water, carbon monoxide and carbon dioxide.
  • the exhaust gas leaves the fuel cell unit 12 via the
  • Anode exhaust gas recirculation 14 and is in turn fed to the materials upstream of the pump 20 and the anode gas processor 16.
  • the air supplied to the fuel cell unit 12 on the cathode side is discharged via an air discharge line 36.
  • the exhaust gas passes through during the return
  • Anode exhaust gas recirculation 14 also the heat exchanger 32 and the other heat exchanger 38.
  • the heat exchanger 32 is a heat balance between the exhaust gas leaving the fuel cell unit 12, and the reformate, which is supplied to the fuel cell unit.
  • the material flow which is supplied to the anode gas processor 16, further preheated is also the heat exchanger 32 and the other heat exchanger 38.
  • the power generation increases in the fuel cell unit 12 and it increasingly diffuses oxygen from the cathode 17 to the anode 15, which in turn increasingly produces water.
  • oxygen is supplied to the fuel cell unit 12 as a function of the power generation on the anode side.
  • the amount of oxygen supplied by the oxygen supply 22 is reduced in proportion to the increasing power generation of the fuel cell unit 12. In essence, this is a continuous adjustment of the amount of oxygen supplied by the oxygen supply 22.
  • the amount of oxygen supplied by the oxygen supply 22 is regulated in stages.
  • the steam reforming takes place at a reforming temperature of about 500 ° C to 550 ° C.
  • steam is recycled for steam reforming, whereby no additional, external water supply is needed.
  • approximately 60% to 75% of the anode exhaust gas is recirculated by the anode exhaust gas recirculation 14.
  • Recirculation rate is regulated by the pump 20.
  • Normal operation means the scheduled operation of the fuel cell device 10 under normal load. Above all, the fuel cell device 10 in normal operation is also able to achieve the maximum possible efficiency.
  • the fuel cell device 10 is operated or started up by the method according to the invention as follows.
  • the catalyst material 28 is heated before reforming.
  • the fuel cell device 10 is supplied during the start-phase both fuel by means of the fuel supply 18 and oxygen by means of the oxygen supply 22, after which a reforming of the fuel-air mixture by partial Oxidation in the anode gas processor 16 is performed.
  • the oxygen-carbon ratio (O / C) is regulated to a value of 1, 2 by means of the valves 24, 26.
  • the corresponding substances contained in the fuel cell unit 10 on the anode side are recirculated by means of the anode exhaust gas recirculation 14 and the pump 20, whereby, inter alia, the fuel cell unit 12 is heated, with the heat produced by the partial oxidation reforming.
  • the fuel cell unit is heated to a sufficiently high temperature, hydrogen is reacted to generate electricity and heat in the fuel cell unit 12 and the transitional phase is initiated.
  • the transition phase both partial oxidation reforming and steam reforming are carried out.
  • the amount of oxygen supplied by the oxygen supply 22 is reduced in proportion to the power generation of the fuel cell unit 12, thereby increasing the steam reforming performance relative to the partial oxidation reforming.
  • an exhaust pipe 40 is attached to the anode exhaust gas recirculation line 14, through which a part of the anode exhaust gas is tapped off and discharged from the fuel cell device 10.
  • FIG. 2 shows a schematic representation of a further exemplary embodiment of the fuel cell device 10 according to the invention. Compared to the embodiment shown in FIG. 1, a further oxygen supply 42 is arranged.
  • At least one reformate is cooled, which is formed by a reforming during one of the operating phases.
  • the cooling of the reformate is made possible by means of an additional heat exchanger 44, which downstream of the anode dengas processor 16 and upstream of the fuel cell unit 12 is arranged.
  • the amount of oxygen supplied via the further oxygen supply 42 is regulated via a further valve 46.
  • a further valve 46 In the illustrated embodiment is
  • the reformate is cooled, which is formed by partial oxidation during the reforming and has a high temperature of about 800 ° C to 1200 ° C. By cooling this reformate is avoided that caused by the high temperature damage in the fuel cell unit 12.
  • the amount of oxygen supplied by the further oxygen supply 42 is reduced. It is reduced depending on the power generation of the fuel cell unit 12.
  • the amount of oxygen supplied by the further oxygen supply 42 is adjusted to the partial oxidation reduction during the transition phase, which is in turn influenced by the amount of oxygen supplied via the oxygen supply 22.
  • oxygen supply 22 and the further oxygen supply 40 are controlled via a common valve.
  • the exhaust line 40 is designed in FIG. 2 such that the air which is supplied to the fuel cell unit 12 on the cathode side via the air supply line 34 is heated by the exhaust gas contained in the exhaust line 40 by means of a further heat exchanger 48. By the heated air in turn, the fuel cell unit 12 is additionally heated on the cathode side.
  • the amount of oxygen supplied via the oxygen supply 22 and / or the further oxygen supply 42 is regulated at least not exclusively as a function of the power generation of the fuel cell unit 12, but as a function of one other physical quantity, such as a temperature, a composition of matter and / or a moisture content. Corresponding variables can be determined at various locations of the fuel cell device 10.
  • the temperature of the reformate could be determined by a temperature sensor downstream of the anode gas processor 16 and upstream of the fuel cell unit 12 and / or the composition of the reformate by a corresponding sensor downstream of the anode gas processor 16 and upstream of the fuel cell unit 12 and / or the moisture content in the exhaust gas by a humidity sensor the anode exhaust gas recirculation line 14 are determined.
  • first, the second and the third operating phase take place not successively, but independently of one another at different times during the operation of the fuel cell device 10. Furthermore, it is conceivable that further operating phases take place with possibly further reforms or types of reforming.

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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention concerne un dispositif de piles à combustible (10) et un procédé pour faire fonctionner un dispositif de piles à combustible (10) comprenant au moins une unité de piles à combustible (12) et au moins une recirculation de gaz d'échappement anodique (14). L'invention a trait à au moins un dispositif de traitement de gaz anodique (16) qui est conçu pour effectuer différents reformages au cours de différentes phases de fonctionnement.
PCT/EP2015/065936 2014-09-18 2015-07-13 Dispositif de piles à combustible comprenant un dispositif de traitement de gaz anodique amélioré WO2016041654A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014218726.5A DE102014218726A1 (de) 2014-09-18 2014-09-18 Brennstoffzellenvorrichtung mit verbessertem Anodengasprozessor
DE102014218726.5 2014-09-18

Publications (1)

Publication Number Publication Date
WO2016041654A1 true WO2016041654A1 (fr) 2016-03-24

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PCT/EP2015/065936 WO2016041654A1 (fr) 2014-09-18 2015-07-13 Dispositif de piles à combustible comprenant un dispositif de traitement de gaz anodique amélioré

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DE (1) DE102014218726A1 (fr)
WO (1) WO2016041654A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT520263A1 (de) * 2017-08-07 2019-02-15 Avl List Gmbh Brennstoffzellensystem mit zumindest einer Hochtemperatur-Brennstoffzelle
AT521650A1 (de) * 2018-08-23 2020-03-15 Avl List Gmbh Brennstoffzellensystem und Verfahren zum Betreiben desselben

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1172876A2 (fr) * 2000-07-11 2002-01-16 XCELLSIS GmbH Pile à combustible avec une unité interne de réformage
EP1393804A1 (fr) 2002-08-26 2004-03-03 Umicore AG & Co. KG Catalyseur multicouche pour réformage à la vapeur autotherme d'hydrocarbures et son utilisation
US20050181247A1 (en) * 2002-05-21 2005-08-18 Ceramic Fuel Cells Limited Fuel cell system
US20060188761A1 (en) * 2005-01-25 2006-08-24 O'brien Christopher J Fuel cell power plants
WO2007137068A1 (fr) * 2006-05-16 2007-11-29 Acumentrics Corporation Système de pile à combustible et son procédé de fonctionnement
EP2416418A1 (fr) * 2009-03-31 2012-02-08 Toto Ltd. Pile à combustible à électrolyte solide
EP2710657A1 (fr) * 2011-05-19 2014-03-26 Honda Motor Co., Ltd. Système de pile à combustible

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1393804U (fr)

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1172876A2 (fr) * 2000-07-11 2002-01-16 XCELLSIS GmbH Pile à combustible avec une unité interne de réformage
US20050181247A1 (en) * 2002-05-21 2005-08-18 Ceramic Fuel Cells Limited Fuel cell system
EP1393804A1 (fr) 2002-08-26 2004-03-03 Umicore AG & Co. KG Catalyseur multicouche pour réformage à la vapeur autotherme d'hydrocarbures et son utilisation
US20060188761A1 (en) * 2005-01-25 2006-08-24 O'brien Christopher J Fuel cell power plants
WO2007137068A1 (fr) * 2006-05-16 2007-11-29 Acumentrics Corporation Système de pile à combustible et son procédé de fonctionnement
EP2416418A1 (fr) * 2009-03-31 2012-02-08 Toto Ltd. Pile à combustible à électrolyte solide
EP2710657A1 (fr) * 2011-05-19 2014-03-26 Honda Motor Co., Ltd. Système de pile à combustible

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT520263A1 (de) * 2017-08-07 2019-02-15 Avl List Gmbh Brennstoffzellensystem mit zumindest einer Hochtemperatur-Brennstoffzelle
AT520263B1 (de) * 2017-08-07 2019-12-15 Avl List Gmbh Brennstoffzellensystem mit zumindest einer Hochtemperatur-Brennstoffzelle
AT521650A1 (de) * 2018-08-23 2020-03-15 Avl List Gmbh Brennstoffzellensystem und Verfahren zum Betreiben desselben
AT521650B1 (de) * 2018-08-23 2020-09-15 Avl List Gmbh Brennstoffzellensystem und Verfahren zum Betreiben desselben

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