WO2003098728A1 - Fuel cell system - Google Patents
Fuel cell system Download PDFInfo
- Publication number
- WO2003098728A1 WO2003098728A1 PCT/AU2003/000609 AU0300609W WO03098728A1 WO 2003098728 A1 WO2003098728 A1 WO 2003098728A1 AU 0300609 W AU0300609 W AU 0300609W WO 03098728 A1 WO03098728 A1 WO 03098728A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fuel cell
- methanator
- methane
- fuel
- supply stream
- Prior art date
Links
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
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of 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
- H01M8/06—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
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- 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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
-
- 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
- H01M8/0637—Direct internal reforming at the anode of the fuel cell
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- 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
-
- 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
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Definitions
- the present invention relates to a method for the thermal management of a fuel cell and to a fuel cell system which facilitates thermal management of a fuel cell.
- the invention also relates to an auxiliary power unit (APU) incorporating the fuel cell system of the invention.
- APU auxiliary power unit
- the present invention provides a method for the thermal management of a fuel cell, which method comprises:
- the way in which the methanator is operated is adjusted in response to fluctuations in the temperature of the fuel cell such that the concentration of methane in the fuel cell supply stream is controlled in order to achieve a desired level of reforming of methane within the fuel cell.
- the methane concentration in the fuel cell supply stream may be controlled by adjusting the temperature at which the methanator is operated.
- a methanator has a particular operating temperature range and this will depend, amongst other things, on the type of catalyst employed.
- the methanator will be operated at a suitable temperature within this operating range to achieve the desired control of methane output.
- the methanator is operated at the low end of the methanator operating temperature range, as this favours methane formation.
- the methanator is run at the high end of the methanator operating temperature range.
- the temperature of the methanator is managed by cooling rather than heating. This is because the fuel supply stream input to the methanator is invariably processed upstream of the methanator in order to generate the reactants necessary for the methanation reaction, and this processing generally takes place at temperatures higher than the temperature at which the methanator would be operated. Indeed, thermodynamically to achieve methanation, the temperature at which the methanator is operated must be lower than that of the upstream processing. Thus, prior to delivery to the methanator, the fuel supply stream is usually cooled and the extent of cooling enables the temperature at which methanation takes place to be controlled.
- the fuel supply stream may be cooled by conventional techniques such as by use of heat exchangers.
- the methanator itself may be cooled by conventional means, for example by air blowers, pipe coils, heat exchange plates and cooling channels provided within the methanator.
- the methanator may be appropriate to insulate the methanator to avoid unwanted or unexpected heat loss (though such loss may be taken into account if the methanator is not well insulated). Unwanted or unexpected loss from the methanator may have a detrimental effect on operation of the fuel cell, particularly under turndown where the load demand on the fuel cell is low and minimal internal reforming of methane is required in order to achieve thermal balance, hi that case the methanator is operated at a (high) temperature which is the same or approximately the same as the temperature at which upstream processing of the fuel supply stream takes place. Operation under such conditions results in minimal or no methane production, as desired.
- the proportion of fuel supply which is allowed to by-pass the methanator may be restricted so that increased methanation takes place, as necessary to achieve thermal balance of the fuel cell under increased load demand.
- Using a methanator by-pass allows the methanator temperature to be suitably managed in order to achieve rapid response in methane production depending on fluctuations in fuel cell temperature on transition between differing load demands.
- the present invention includes this methanator by-pass as part of the overall system design.
- the catalyst comprises platinum, palladium, ruthenium or rhodium, supported on a refractory metal oxide such as alumina, in a suitable form such as a monolithic body.
- the partial oxidation catalyst or autothermal reformer catalyst may be an oxide-based catalyst which is more tolerant to sulfur containing fuels.
- the catalyst used to effect catalytic partial oxidation is effective in the presence of sulfur compounds, although sulphur removal is required to prevent poisoning of the methanator catalyst and/or the anode.
- the temperature at which catalytic partial oxidation takes place is typically 400 to 1000°C, for example 800 to 900°C.
- Partial oxidation is purely a thermal process, without catalysis.
- the POX reactor may be fitted with a heated (platinum) element to assist cold start-up until sufficient heat has been generated to raise the temperature of the reactor to above the light-off temperature of diesel.
- the fuel is a hydrocarbon fuel including organic-sulfur containing compounds such as thiophenes and mercaptans, and other carbon-containing sulphur compunds such as carbonyl sulphide and carbon disulphide, these will be converted to sulphur dioxide and hydrogen sulfide in the upstream processor.
- desulfurisation will be necessary to remove hydrogen sulfide which would otherwise cause poisoning of the catalyst in the methanator and/or the anode of the fuel cell.
- the processed fuel from the upstream reformer is cooled to about 400°C prior to delivery to the adsorbent bed.
- the desulfurisation unit is operated under conventional operating conditions.
- such a fuel may be passed through a fuel sulfur trap upstream of the ATR or CPOX. This will be particularly preferable if the ATR or CPOX catalyst is not tolerant to sulphur levels present in the fuel.
- the sulfur content of the stream Prior to delivery of the fuel cell supply stream to the fuel cell the sulfur content of the stream is typically reduced to a level of less than about 1 part per million by weight, and preferably to less than 0.2 parts per million by weight.
- the autothermal reformer, CPOX or POX reactor is provided in communication with any sulfur removal unit, the position of the latter being dependent on the type of fuel used.
- the methanator of the system is provided upstream of and in communication with a fuel cell, the methanator output (the fuel cell supply stream) being delivered to the anode of the fuel cell.
- Methane present in the fuel cell supply stream is reformed at the anode of the fuel cell.
- the anode may comprise a metallic component such as nickel, cobalt, iron or other transition metals, supported on a suitable material such as zirconia, ceria, samaria, or other rare-earth oxides, to catalyse the methane reforming reaction and the fuel-cell reaction.
- the anode may contain additional materials like magnesium oxide or other alkaline oxides as promoters.
- the reforming anode catalyst may be provided in fuel flow channels within the anode side of the fuel cell.
- the fuel cell and its associated assembly can take any suitable form, a solid oxide fuel cell (SOFC) or molten carbonate fuel cell (MCFC).
- SOFC solid oxide fuel cell
- MCFC molten carbonate fuel cell
- the fuel cell operates at a temperature which is sufficient to provide essentially substantial conversion of the methane in the internal reforming reaction. This maximises the efficiency of the thermal management system.
- the reforming catalyst provided in the fuel cell has capacity to reform the maximum methane concentration likely to be provided to the fuel cell during operation thereof. This also contributes to the efficiency of the fuel cell system of the present invention.
- Figure 1 shows a fuel cell system in which a fuel stream (1) comprising volatile higher C 2+ hydrocarbons (and organic sulfur-containing compounds) is delivered via a pump (2) to an autothermal reformer (3).
- a fuel stream (1) comprising volatile higher C 2+ hydrocarbons (and organic sulfur-containing compounds) is delivered via a pump (2) to an autothermal reformer (3).
- the fuel Prior to delivery to the autothermal reformer (3), the fuel is vaporised using an electrically heated vaporiser (4) operating at an appropriate temperature of about 200°C.
- Air (5) is also delivered to the autothermal reformer.
- the autothermal reformer (3) operates at a temperature of around 600°C depending upon the chosen catalyst and its activity, and produces a processed fuel stream comprising hydrogen and a carbon oxide or oxides.
- the processed fuel stream is then delivered via a heat exchanger (6) to a desulfuriser unit (7) comprising a ZnO adsorbent bed.
- the desulfuriser unit (7) is operated at about 400°C
- the resultant desulfurised fuel stream is then delivered to a methanator (8) operated at a temperature of about 400°C. In this case cooling of fuel stream to the methanator (8) is not required. If the methanator (8) is operated at a temperature lower than that of the fuel output of the desulfuriser unit (7) cooling will be required. As the reactions in the methanator are exothennic it may be necessary to cool the methanator even if the required methanator temperature is above that of the desulfuriser unit. In the methanator (8) hydrogen and a carbon oxide or oxides are reacted over a suitable catalyst to produce methane.
- the system includes a methanator by-pass (8A) which allows the desulfurised fuel stream to be diverted around the methanator.
- a portion of the anode waste stream (13) may be used to pre-heat the fuel cell supply stream (1) by means of a heat exchanger (10). That portion may then be delivered to a catalytic oxidiser (16). A portion of the anode waste stream may also be mixed with the desulfurised fuel stream supplied to the methanator and/or with the fuel cell supply stream prior to delivery of the latter to the anode (11).
- the cathode (17) of the fuel cell stack (12) is supplied with oxidant (air) (18) which is preheated using heat exchangers (6, 19).
- the cathode waste stream (20) is fed to the catalytic oxidiser (16) in heat exchange with the incoming oxidant supply at heat exchange (19).
- the temperature of the fuel cell stack (12) is monitored using a thermocouple or other means (not shown) and the methanator output controlled in order to provide an appropriate amount of methane to the anode (11) such that internal reforming takes place to the extent necessary to achieve thermal balance of the fuel cell.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004506114A JP4515253B2 (en) | 2002-05-21 | 2003-05-20 | Fuel cell system |
AT03722060T ATE473527T1 (en) | 2002-05-21 | 2003-05-20 | FUEL CELL SYSTEM |
CA2486706A CA2486706C (en) | 2002-05-21 | 2003-05-20 | Method and system for thermal management of a fuel cell |
AU2003229365A AU2003229365B2 (en) | 2002-05-21 | 2003-05-20 | Fuel cell system |
US10/514,842 US8057947B2 (en) | 2002-05-21 | 2003-05-20 | Thermal management of a fuel cell system |
EP03722060A EP1506589B1 (en) | 2002-05-21 | 2003-05-20 | Fuel cell system |
DE60333283T DE60333283D1 (en) | 2002-05-21 | 2003-05-20 | FUEL CELL SYSTEM |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPS2448 | 2002-05-21 | ||
AUPS2448A AUPS244802A0 (en) | 2002-05-21 | 2002-05-21 | Fuel cell system |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003098728A1 true WO2003098728A1 (en) | 2003-11-27 |
Family
ID=3836014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2003/000609 WO2003098728A1 (en) | 2002-05-21 | 2003-05-20 | Fuel cell system |
Country Status (8)
Country | Link |
---|---|
US (1) | US8057947B2 (en) |
EP (1) | EP1506589B1 (en) |
JP (1) | JP4515253B2 (en) |
AT (1) | ATE473527T1 (en) |
AU (2) | AUPS244802A0 (en) |
CA (1) | CA2486706C (en) |
DE (1) | DE60333283D1 (en) |
WO (1) | WO2003098728A1 (en) |
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JP2006261025A (en) * | 2005-03-18 | 2006-09-28 | Hitachi Ltd | Fuel cell power generation system and its control method |
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- 2003-05-20 JP JP2004506114A patent/JP4515253B2/en not_active Expired - Fee Related
- 2003-05-20 US US10/514,842 patent/US8057947B2/en not_active Expired - Fee Related
- 2003-05-20 DE DE60333283T patent/DE60333283D1/en not_active Expired - Lifetime
- 2003-05-20 CA CA2486706A patent/CA2486706C/en not_active Expired - Fee Related
- 2003-05-20 AT AT03722060T patent/ATE473527T1/en not_active IP Right Cessation
- 2003-05-20 EP EP03722060A patent/EP1506589B1/en not_active Expired - Lifetime
- 2003-05-20 AU AU2003229365A patent/AU2003229365B2/en not_active Ceased
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Cited By (21)
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EP1416566A2 (en) * | 2002-10-12 | 2004-05-06 | Volkswagen Aktiengesellschaft | Fuel cell system, particularly for automobiles |
EP1416566A3 (en) * | 2002-10-12 | 2006-12-20 | Volkswagen Aktiengesellschaft | Fuel cell system, particularly for automobiles |
US10283792B2 (en) | 2004-02-10 | 2019-05-07 | Ceres Intellectual Property Company Limited | Method and apparatus for operating a solid-oxide fuel cell stack with a mixed ionic/electronic conducting electrolyte |
JP2015084333A (en) * | 2004-02-10 | 2015-04-30 | セレス インテレクチュアル プロパティー カンパニー リミテッド | Method and apparatus for operating solid electrolyte fuel cell stack using mixed ionic/electronic conducting electrolyte |
JP2007522643A (en) * | 2004-02-10 | 2007-08-09 | セレス・パワー・リミテッド | Method and apparatus for operating a solid electrolyte fuel cell stack using a mixed ionic / electronic conducting electrolyte |
JP2013058494A (en) * | 2004-02-10 | 2013-03-28 | Ceres Intellectual Property Co Ltd | Method and apparatus for operating solid-electrolyte fuel cell stack using mixed ionic/electronic conducting electrolyte |
US7785380B2 (en) | 2004-04-02 | 2010-08-31 | Powercell Sweden Ab | Method for removing sulfur from a hydrocarbon fuel |
US7618598B2 (en) | 2004-11-29 | 2009-11-17 | Modine Manufacturing Company | Catalytic reactor/heat exchanger |
DE102005054713A1 (en) * | 2004-11-29 | 2006-06-08 | Modine Manufacturing Co., Racine | Heat exchanger device |
JP2006261025A (en) * | 2005-03-18 | 2006-09-28 | Hitachi Ltd | Fuel cell power generation system and its control method |
EP1739777A3 (en) * | 2005-06-28 | 2009-01-21 | J. Eberspächer GmbH Co. KG | Fuel cell system for vehicles |
US8053139B2 (en) | 2006-03-31 | 2011-11-08 | Corning Incorporated | SOFC thermal management via direct injection |
WO2007137068A1 (en) * | 2006-05-16 | 2007-11-29 | Acumentrics Corporation | Fuel cell system and operting method thereof |
WO2008057427A1 (en) * | 2006-11-08 | 2008-05-15 | Saudi Arabian Oil Company | A process for the conversion of oil-based liquid fuels to a fuel mixture suitable for use in solid oxide fuel cell applications |
US8123826B2 (en) | 2006-11-08 | 2012-02-28 | Saudi Arabian Oil Company | Process for the conversion of oil-based liquid fuels to a fuel mixture suitable for use in solid oxide fuel cell applications |
WO2008107457A1 (en) * | 2007-03-06 | 2008-09-12 | Ceramtec Ag | Method for the environmentally sound disposal of air/solvent mixtures using a fuel cell system and recovery unit |
US8173082B1 (en) | 2007-05-14 | 2012-05-08 | Gas Technology Institute | JP-8 fuel processor system |
EP1998398A3 (en) * | 2007-05-22 | 2009-03-18 | Delphi Technologies, Inc. | Method and apparatus for fueling a solid oxide fuel cell stack |
WO2013117810A1 (en) * | 2012-02-10 | 2013-08-15 | Convion Oy | Method and arrangement for utilizing recirculation for high temperature fuel cell system |
KR101563455B1 (en) | 2012-02-10 | 2015-10-26 | 콘비온 오와이 | Method and arrangement for utilizing recirculation for high temperature fuel cell system |
US9496567B2 (en) | 2012-02-10 | 2016-11-15 | Convion Oy | Method and arrangement for utilizing recirculation for high temperature fuel cell system |
Also Published As
Publication number | Publication date |
---|---|
EP1506589A4 (en) | 2007-11-07 |
JP2005535068A (en) | 2005-11-17 |
ATE473527T1 (en) | 2010-07-15 |
AUPS244802A0 (en) | 2002-06-13 |
EP1506589B1 (en) | 2010-07-07 |
AU2003229365B2 (en) | 2008-10-16 |
JP4515253B2 (en) | 2010-07-28 |
CA2486706C (en) | 2011-04-19 |
US20050181247A1 (en) | 2005-08-18 |
EP1506589A1 (en) | 2005-02-16 |
AU2003229365A1 (en) | 2003-12-02 |
US8057947B2 (en) | 2011-11-15 |
DE60333283D1 (en) | 2010-08-19 |
CA2486706A1 (en) | 2003-11-27 |
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