WO2012076136A1 - Procédé permettant de faire fonctionner un système de piles à combustible et système de piles à combustible - Google Patents

Procédé permettant de faire fonctionner un système de piles à combustible et système de piles à combustible Download PDF

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Publication number
WO2012076136A1
WO2012076136A1 PCT/EP2011/006057 EP2011006057W WO2012076136A1 WO 2012076136 A1 WO2012076136 A1 WO 2012076136A1 EP 2011006057 W EP2011006057 W EP 2011006057W WO 2012076136 A1 WO2012076136 A1 WO 2012076136A1
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WO
WIPO (PCT)
Prior art keywords
fuel cell
burner
fuel
reformer
gas
Prior art date
Application number
PCT/EP2011/006057
Other languages
German (de)
English (en)
Inventor
Steffen Wieland
Bernhard Seyfang
Original Assignee
Enymotion 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 Enymotion Gmbh filed Critical Enymotion Gmbh
Publication of WO2012076136A1 publication Critical patent/WO2012076136A1/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
    • H01M8/04231—Purging of the reactants
    • 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 operating a fuel cell system.
  • electrical energy is generated chemically.
  • the fuel cell is supplied with a continuous stream of a hydrogen-containing gas and a continuous stream of an oxidizing agent (usually atmospheric oxygen).
  • an oxidizing agent usually atmospheric oxygen.
  • water is produced as an exhaust gas product.
  • the hydrogen is often generated in situ from a hydrocarbonaceous fuel, particularly in portable fuel cell systems.
  • liquefied petroleum gas (LPG) can be used as the hydrocarbon-containing fuel, which is particularly suitable for portable fuel cell systems.
  • the main components of LPG are propane and n-butane.
  • "Fuel in the context of this application, however, can be any starting substance which can be used for the production of hydrogen.
  • the other reactants required for the reaction, in particular oxygen (air) or water, however, are supplied separately to the respective components of the fuel cell system and are not part of the fuel.
  • the fuel cell is preceded by a reformer in which a chemical conversion of the fuel into a hydrogen-containing gas takes place.
  • the reformer can in this case, for example, by the process of steam reforming, partial oxidation or autothermal reforming work.
  • the anode of the fuel cell is supplied by the reformer with a hydrogen-containing gas in an optimum state for the respective system. added composition.
  • the cathode is oxygen, usually supplied as part of ambient air.
  • the object of the invention is to present an optimized operating method for which the complexity of the fuel cell system does not have to be significantly increased.
  • inert gases are understood to mean any gas which is harmless to the operation of the fuel cell, mainly nitrogen, carbon dioxide and water, but it is also possible under certain conditions to use gases other than purge gas which under these conditions react neither with hydrogen or oxygen nor with the materials used in the fuel cell system, so behave inertly under these circumstances.
  • the fuel itself may be used, particularly when the fuel is LPG.
  • the fuel behaves under certain conditions like an inert gas.
  • ambient air for the fuel cell can be uncritically replaced by fuel.
  • the reformer hydrogen-containing gas instead of the fuel flow. In this way, the fuel cell system enters the rated operation.
  • the hydrogen-containing gas can be gradually replaced by the (oxygen-free) fuel.
  • the fuel can also be used to flush out the remaining water in the fuel cell system.
  • the fuel cell is flushed with a gas stream consisting essentially of inert gases such as nitrogen, carbon dioxide or water.
  • the exhaust gas of the fuel cell is first reacted in the burner substantially in inert gases, and this emerging from the burner gas stream is passed through an exhaust gas recirculation for purging by the fuel cell.
  • the burner present in the system which is connected downstream of the fuel cell and converts the hydrogen-containing exhaust gas of the fuel cell and which also operates in rated operation, is used in startup and shutdown mode to produce a gas stream which is preferably completely inert gases, for flushing the system is used by unwanted gases such as hydrogen and water.
  • the inert gas stream produced by the burner can also be passed through the reformer and used to purge the reformer.
  • the combustion air ratio ⁇ describes the ratio between the amount of air supplied and the amount of air required for the stoichiometric conversion. With a ⁇ of 1, the fuel is completely stoichiometrically reacted with the amount of air supplied.
  • the burner with an air ratio of ⁇ - ⁇ 1 operated in a first rinsing step. In this way, it is ensured that no oxygen enters the fuel cell system, in particular into the anode of the fuel cell, in which hydrogen is still present at the end of nominal operation.
  • the first purge step may be performed until the hydrogen has been substantially removed from the fuel cell.
  • the burner can be operated with an air ratio of ⁇ 1, so that complete combustion of the fuel-containing gas supplied to the burner takes place.
  • the carbon monoxide contained in the gas stream is essentially completely converted in the burner.
  • a possible excess of oxygen, which passes through the fuel cell with the purge gas is now not critical, since no more hydrogen is present in the fuel cell.
  • the excess air can be used to discharge the water still in the system. It is particularly advantageous if the burner has heated the inert gas, so that the existing water can be better absorbed.
  • the supplied scavenging air can be preheated in the reformer and / or in the burner, wherein both components are preferably already switched off in this case and their residual heat is utilized.
  • the reformer already turn off and only use its residual heat.
  • the reformer be operated in a mode in which it generates almost exclusively inert gases.
  • the burner converts the hydrogen-containing exhaust gases of the anode of the fuel cell in rated operation. In deviating from normal operation operating conditions, in particular the on and. Abfahrphase, it is possible to supply the burner directly generated by the gas reformer gas via a bypass line bypassing the fuel cell. If a larger amount of purge gas is required, it is also possible to supply hydrocarbon-containing fuel to the burner from a storage tank of the fuel cell system.
  • the invention also relates to a fuel cell system in which the methods described above can be used.
  • the invention in a first alternative, relates to a fuel cell system which can be flushed with fuel, the fuel cell system having at least one fuel cell with an anode and a cathode, a hydrogen-containing gas reformer, a burner connected downstream of the fuel cell, and a controller, and the fuel cell system is operable in a normal operation and a startup or shutdown operation.
  • the controller switchable flow connection between a fuel tank and the fuel cell, so that fuel can be passed through the anode and / or the cathode.
  • the cathode can be cleaned in a simple manner when starting air and when driving off hydrogen and water.
  • the fuel is preferably conducted completely via preferably switchable lines to the burner and implemented therein, so that substantially only water and carbon dioxide enter the environment during the rinsing steps with fuel as purge gas.
  • the fuel cell system has at least one fuel cell, a reformer for generating hydrogen-containing gas, a burner connected downstream of the fuel cell, and a controller.
  • the fuel cell system can be operated in a nominal mode and in a startup or shutdown mode.
  • a return line from the burner to a line leading to the fuel cell is provided and the controller is arranged to operate the burner in a startup and / or shutdown mode to produce substantially inert gases.
  • the controller connects the return line in this case via a valve with the line leading to the fuel cell for purging the fuel cell. It is advantageous here that no further components (with the exception of the return line) must be provided in the system, which keeps both the costs and the installation space of the system low.
  • FIG. 1 is a schematic representation of a first embodiment of a fuel cell system according to the invention for carrying out a method according to the invention
  • FIG. 2 shows a second embodiment of a fuel cell system according to the invention for carrying out a method according to the invention
  • FIG. 3 shows a third embodiment of a fuel cell system according to the invention for carrying out a method according to the invention.
  • FIG. 1 shows a fuel cell system 10 with a fuel cell 12, which in a known manner has an anode 14 and a cathode 16, and which here represents a whole stack of fuel cells.
  • the fuel cell 12 is supplied via a supply line 18 with a hydrogen-containing gas, which is generated in a reformer 20 by a chemical reaction by autothermal reforming from a hydrocarbon-containing fuel from a storage tank 22 in a known way.
  • the reformer 20 also air and water are supplied, which are needed for autothermal reforming.
  • the cathode 16 of the fuel cell 12 is supplied with oxygen via an air supply that conducts ambient air to the cathode 16 (not shown).
  • an air supply that conducts ambient air to the cathode 16 (not shown).
  • the hydrogen-containing off-gas derived from the anode 14 will be delivered via a conduit 24 led to a burner 26.
  • the hydrogen-containing exhaust gas is catalytically reacted with air and then discharged via an exhaust line 28 into the environment of the fuel cell system.
  • a return line 30 which opens to the reformer 20 or alternatively or in combination downstream of the reformer 20 in the conduit 18.
  • a valve 32 offers the possibility to direct the exhaust gas flow to the burner 26 either completely or partially through the return line 30.
  • Exhaust gas recirculation may be active, e.g. by a pump or venturi.
  • a controller 34 is connected to the valve 32 and to the burner 26 and can regulate the valve position and the burner power, for example by adjusting the air supply to the burner 26.
  • bypass line 36 is provided, by means of which the fuel cell 12 can be bridged.
  • the bypass line 36 branches off from the supply line 18, bypasses the fuel cell 12 and leads downstream of the fuel cell 12 into the line 24. Via a valve 38, the gas flow to the fuel cell 12 can be diverted either completely or partially into the bypass line 36. In all cases in which a gas flow is only partially guided via the return line 30 and the bypass line 36, only the volume of the gas stream is reduced, but not changed its composition.
  • hydrocarbonaceous fuel such as liquefied petroleum gas (LPG)
  • LPG liquefied petroleum gas
  • hydrocarbonaceous fuel is directed from the storage tank 22 to the reformer 20 where hydrogen-containing gas is supplied under supply of air and water which is passed through the conduit 18 to the anode 14 of the fuel cell 12 (the bypass conduit 36) completely closed in the example described here, so that all the gas supplied by the reformer 20 reaches the anode 14).
  • the fuel cell 12 a large part of the hydrogen contained in the gas stream is reacted, and the exhaust gas containing the remaining hydrogen is passed via the line 24 to the burner 26.
  • the residual hydrogen is completely ( ⁇ > 1) burned with supply of ambient air (not shown) in this example, and the resulting exhaust gases are discharged via the exhaust pipe 28 to the outside.
  • the exhaust gases contain no more hydrogen and carbon monoxide, but may well have unreacted atmospheric oxygen.
  • the return line 30 is closed, so that no exhaust gas is returned to the reformer 20.
  • the fuel cell system 10 In the start-up phase of the fuel cell system 10 (which corresponds to a first abnormal operation state), the fuel cell system 10 is started after being out of operation for a while. This means that in the fuel cell 12 and also in the anode 14 ambient air and thus oxygen is present.
  • the fuel cell system including the fuel cell 12 In order to remove these disturbing for the rated operation of the fuel cell 2 gases from the system 10, the fuel cell system including the fuel cell 12 is purged with a purge gas until the interfering gases fall below a predetermined concentration.
  • the reformer 20 In a first phase, the reformer 20 is operated in such a way that it generates hydrogen-containing gas.
  • This gas stream is passed completely through the valve 38 and the bypass line 36 past the fuel cell 12 and thus passes directly into the burner 26.
  • the combustible constituents of the gas are completely converted ( ⁇ > 1).
  • the exhaust gases are discharged into the environment. This phase is mainly used to heat the components of the fuel cell system 10th
  • the burner 26 is operated via the controller 34 in a mode that its exhaust gas consists essentially of inert gases, so no oxygen is contained ( ⁇ .s 1, preferably 0.9 .s ⁇ ⁇ 1).
  • the reformer 20 is turned off or is also operated in a mode where it produces substantially inert gases.
  • the air supply to the reformer 20 can be adjusted so that substantially inert gases are generated in the reformer 20.
  • the gas stream leaving the burner 26 contains virtually exclusively inert gases (nitrogen, carbon dioxide, water) which do not contain any gases harmful to the fuel cell 12 or other components of the system.
  • the valve 32 is switched via the controller 34 so that the exhaust gas flow to the burner 26 is wholly or partially recycled via the return line 30.
  • the valve 32 is switched so that this gas flow is fed via the return line 30 upstream of the reformer 20 or bypassing the reformer 20 downstream in the conduit 18.
  • the exhaust gas from the burner 26 is directed to rinse through the anode 14 of the fuel cell 12.
  • bypass line 36 is completely or partially closed via the valve 38 and the gas flow wholly or partially passed through the fuel cell 12 to flush it with the inert gases, so that the anode 14 is released from any atmospheric oxygen. After this rinsing cycle, the anode 14 is thus oxygen-free.
  • the reformer 20 could also be operated so that substantially only inert gases are generated. This first flushing step also ensures that the burner 26 and the reformer 20 reach their operating temperature more quickly through the return of the hot exhaust gas.
  • the exhaust gas recirculation is stopped again and the exhaust gas is discharged to the burner 26 in the environment.
  • the burner 26 is adjusted so that the hydrogen-containing exhaust gases supplied to it are completely burned ( ⁇ > 1).
  • the reformer 20 is switched to the mode in which it provides the optimal gas composition for the fuel cell 12. Eventually, for a short time (a few seconds), the gas flow to the reformer 20 can be bypassed via the bypass line 36 to the fuel cell until the gas composition is optimal.
  • the gas flow from the reformer 20 is completely conducted via the fuel cell 12.
  • the exhaust gas is passed through the exhaust pipe 28 to the outside.
  • the fuel cell system 10 is in its normal operation.
  • the valve 32 is switched via the controller 34 so that the exhaust gases are conducted via the return line 30 back to the reformer 20 or to the fuel cell 12.
  • the burner 26 is operated with a combustion air ratio of ⁇ ⁇ 1 (preferably 0.9 ⁇ ⁇ 1), so that no oxygen is contained in the exhaust gas stream downstream of the burner 26.
  • the exhaust stream contains virtually only for the fuel cell 12 inert gases (nitrogen, carbon dioxide, water).
  • the reformer 20 may either be already switched off or it may be operated in a mode in which it also produces practically only inert gases.
  • the fuel cell 12, especially the anode 14, is rinsed with these inert gases and the hydrogen discharged from the anode 14 is converted into water in the burner 26.
  • a second rinsing step can be carried out, in which the burner is operated in an air ratio ⁇ 2 1 (preferably 1> ⁇ 51, 1), so that all exhaust gases in the burner 26 are completely converted, in particular possibly still existing hydrogen and carbon monoxide.
  • the exhaust gas contains oxygen.
  • the exhaust stream is also passed through the reformer 20, which may already be switched off, but the residual heat is used to heat the exhaust stream.
  • the heated exhaust gas absorbs the water in the fuel cell system 10, so that it can finally be transported through the exhaust pipe 28 to the outside. It is possible to recirculate the exhaust only partially. After completion of this second rinsing step, the burner 26 and the reformer 20 are turned off.
  • FIG. 2 shows a second embodiment of the fuel cell system 100.
  • a second burner 136 is provided in addition to the burner 26, which is supplied via the storage tank 22 with hydrocarbon-containing fuel.
  • This burner 136 is mainly used to heat system components, such as the fuel cell 12, in the start-up phase. But he can also be used for that be generated additionally inert gases, if the exhaust gas of the fuel cell 12 contains too little hydrogen.
  • the inert gases generated in the burner 136 are introduced downstream of the burner 26, but upstream of the valve 32 and then transported on the return line 30 as described above.
  • the burner 136 (and any other burner) is also connected to the controller 34 and is operated analogously to the burner 26 with the respective desired air ratio ⁇ .
  • Such supply of the burner 26 with hydrocarbon-containing fuel is especially for the start-up phase of the system when the reformer 20 is still off, for generating purge gas for the lines, the reformer and the fuel cell 12 is advantageous.
  • FIG. 3 shows a fuel cell system 200 that is similar in construction to the systems just described, but designed to allow the fuel cell 12 (both anode 14 and cathode 16) to be purged with the same fuel that is from the fuel tank 22 is also supplied to the reformer 20 for generating the hydrogen-containing gas.
  • the fuel here liquefied gas
  • the fuel can be conducted to the anode 14 and through it to the burner 26.
  • fuel may be directed from the fuel tank 22 through the cathode 16 to the burner 26.
  • the air supply to the cathode 16 is preferably switched off.
  • all system components through which flow is maintained at a temperature below the ignition temperature of the fuel, and / or it is ensured that these components are free of oxygen at elevated temperatures.
  • the controller 34 controls the gas flows as in the previously described embodiments.
  • the reformer 20 could also be operated in another mode (partial oxidation or steam reforming). Likewise, it is of course possible to downstream one or more purification stages the reformer 20 and to integrate into these.

Abstract

L'invention concerne un procédé permettant de faire fonctionner un système de piles à combustible, comprenant au moins une pile à combustible (12), un reformeur (20) destiné à produire un gaz contenant de l'hydrogène et un brûleur (26) monté en aval de la pile à combustible (12). Dans un état de fonctionnement s'écartant du fonctionnement normal, la pile à combustible (12) est balayée par un fluide de balayage, le fluide de balayage étant constitué du combustible et/ou d'un courant de gaz constitué sensiblement de gaz inertes. Le gaz d'échappement de la pile à combustible (12) est sensiblement transformé dans le brûleur (26) en gaz inertes, et ce courant de gaz sortant du brûleur (26) est acheminé à travers la pile à combustible (12) par une conduite de recirculation des gaz d'échappement pour le balayage.
PCT/EP2011/006057 2010-12-06 2011-12-02 Procédé permettant de faire fonctionner un système de piles à combustible et système de piles à combustible WO2012076136A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010053572.9 2010-12-06
DE102010053572.9A DE102010053572B4 (de) 2010-12-06 2010-12-06 Verfahren zum Betrieb eines Brennstoffzellensystems

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WO2012076136A1 true WO2012076136A1 (fr) 2012-06-14

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WO (1) WO2012076136A1 (fr)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06203865A (ja) * 1993-01-06 1994-07-22 Sanyo Electric Co Ltd 燃料電池システム
US5648182A (en) * 1994-08-31 1997-07-15 Kabushikikaisha Eqous Research Fuel cell power generation system
JP2002050372A (ja) * 2000-08-04 2002-02-15 Honda Motor Co Ltd 燃料電池用パージ装置
US20030072978A1 (en) 2001-10-11 2003-04-17 Meyer Alfred P. Procedure for purging a fuel cell system with inert gas made from organic fuel
EP1386883A1 (fr) * 2002-08-02 2004-02-04 Truma Gerätetechnik GmbH & Co. Système comprenant un réformeur et une pile à combustible et procédé pour le démarrage et l'arrêt dudit système
DE10257212A1 (de) * 2002-12-07 2004-06-24 Volkswagen Ag Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems
EP1521325A2 (fr) * 2003-10-01 2005-04-06 Matsushita Electric Industrial Co., Ltd. Système de pile à combustible avec un detecteur de gaz
WO2005036668A2 (fr) * 2003-09-17 2005-04-21 General Motors Corporation Mise en route, arret et evacuation d'une pile a combustible au moyen d'une chambre de combustion stoechiometrique fonctionnant par etapes
DE102005030909A1 (de) * 2005-06-30 2007-01-04 Viessmann Werke Gmbh & Co Kg Verfahren zum Starten und Abschalten einer Brennstoffzellenanlage
EP1760814A2 (fr) * 2005-09-05 2007-03-07 LG Electronics Inc. Procédé de purge d'un système de piles à combustible
US20070248856A1 (en) * 2004-10-15 2007-10-25 Tetsuya Ueda Fuel Cell System and Operating Method Thereof
EP1892783A1 (fr) * 2005-02-18 2008-02-27 Matsushita Electric Industrial Co., Ltd. Système à pile à combustible et procédé d utilisation idoine
WO2008150524A2 (fr) * 2007-06-04 2008-12-11 Bloom Energy Corporation Structure pour le démarrage et l'arrêt d'un système de pile à combustible à haute température
US20100047643A1 (en) * 2007-09-21 2010-02-25 Akinori Yukimasa Fuel cell system
US20100183933A1 (en) * 2009-01-22 2010-07-22 Samsung Electronics Co., Ltd. Fuel cell system and method of operating the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4537839A (en) * 1982-11-23 1985-08-27 Johnson Matthey Public Limited Company Fuel cell and method of purging a fuel cell

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06203865A (ja) * 1993-01-06 1994-07-22 Sanyo Electric Co Ltd 燃料電池システム
US5648182A (en) * 1994-08-31 1997-07-15 Kabushikikaisha Eqous Research Fuel cell power generation system
JP2002050372A (ja) * 2000-08-04 2002-02-15 Honda Motor Co Ltd 燃料電池用パージ装置
US20030072978A1 (en) 2001-10-11 2003-04-17 Meyer Alfred P. Procedure for purging a fuel cell system with inert gas made from organic fuel
EP1386883A1 (fr) * 2002-08-02 2004-02-04 Truma Gerätetechnik GmbH & Co. Système comprenant un réformeur et une pile à combustible et procédé pour le démarrage et l'arrêt dudit système
DE10257212A1 (de) * 2002-12-07 2004-06-24 Volkswagen Ag Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems
WO2005036668A2 (fr) * 2003-09-17 2005-04-21 General Motors Corporation Mise en route, arret et evacuation d'une pile a combustible au moyen d'une chambre de combustion stoechiometrique fonctionnant par etapes
EP1521325A2 (fr) * 2003-10-01 2005-04-06 Matsushita Electric Industrial Co., Ltd. Système de pile à combustible avec un detecteur de gaz
US20070248856A1 (en) * 2004-10-15 2007-10-25 Tetsuya Ueda Fuel Cell System and Operating Method Thereof
EP1892783A1 (fr) * 2005-02-18 2008-02-27 Matsushita Electric Industrial Co., Ltd. Système à pile à combustible et procédé d utilisation idoine
DE102005030909A1 (de) * 2005-06-30 2007-01-04 Viessmann Werke Gmbh & Co Kg Verfahren zum Starten und Abschalten einer Brennstoffzellenanlage
EP1760814A2 (fr) * 2005-09-05 2007-03-07 LG Electronics Inc. Procédé de purge d'un système de piles à combustible
WO2008150524A2 (fr) * 2007-06-04 2008-12-11 Bloom Energy Corporation Structure pour le démarrage et l'arrêt d'un système de pile à combustible à haute température
US20100047643A1 (en) * 2007-09-21 2010-02-25 Akinori Yukimasa Fuel cell system
US20100183933A1 (en) * 2009-01-22 2010-07-22 Samsung Electronics Co., Ltd. Fuel cell system and method of operating the same

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