WO2007077791A1 - Pile a combustible a oxyde solide a reformage interne indirect - Google Patents

Pile a combustible a oxyde solide a reformage interne indirect Download PDF

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Publication number
WO2007077791A1
WO2007077791A1 PCT/JP2006/325772 JP2006325772W WO2007077791A1 WO 2007077791 A1 WO2007077791 A1 WO 2007077791A1 JP 2006325772 W JP2006325772 W JP 2006325772W WO 2007077791 A1 WO2007077791 A1 WO 2007077791A1
Authority
WO
WIPO (PCT)
Prior art keywords
reforming
reformer
fuel cell
solid oxide
oxide fuel
Prior art date
Application number
PCT/JP2006/325772
Other languages
English (en)
Japanese (ja)
Inventor
Yasushi Mizuno
Susumu Hatada
Iwao Anzai
Original Assignee
Nippon Oil Corporation
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 Nippon Oil Corporation filed Critical Nippon Oil Corporation
Publication of WO2007077791A1 publication Critical patent/WO2007077791A1/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
    • H01M8/06—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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 present invention relates to a solid oxide fuel cell, and more particularly to an indirect internal reforming solid oxide fuel cell having a reformer in the vicinity of the fuel cell.
  • Patent Document 1 Japanese Patent Laid-Open No. 2002-358997
  • An object of the present invention is to stably operate an indirect internal reforming solid oxide fuel cell using kerosene as a reforming raw material without lowering efficiency even when operating conditions fluctuate.
  • An indirect internal reforming type solid oxide fuel cell that can be manufactured is provided.
  • a reformer capable of reforming kerosene, a solid oxide fuel cell using a reformed gas obtained from the reformer as a fuel, and a panner for heating the reformer
  • the reformer has a double pipe structure consisting of an outer pipe and an inner pipe,
  • a space between the outer tube and the inner tube is filled with a reforming catalyst capable of steam reforming kerosene, and the panner is connected to one end of the inner tube,
  • the reformer is arranged at a position where the outer surface of the outer tube receives solid oxide fuel cell power thermal radiation.
  • An indirect internal reforming solid oxide fuel cell is provided.
  • the reformer may have a plurality of the double-pipe structures.
  • the reforming catalyst may include a reforming catalyst having kerosene oxidation activity.
  • an indirect internal reforming solid oxide fuel cell using kerosene as a reforming raw material can be stably operated without lowering efficiency even when operating conditions fluctuate.
  • An indirect internal reforming solid oxide fuel cell is provided.
  • FIG. 1 is a schematic diagram showing an example of an indirect internal reforming SOFC of the present invention.
  • Solid oxide fuel cell 3a Anode
  • a reformed gas that is a gas containing hydrogen is produced from kerosene that is a reforming raw material by a steam reforming reaction.
  • partial oxidation reforming reaction may be accompanied at this time, steam reforming is made dominant from the viewpoint of efficiently producing hydrogen. Therefore, in the reformer, the reaction becomes endothermic in overall.
  • the reformer has a double tube structure formed of an outer tube and an inner tube. Therefore, the reformer has two spaces, a space between the outer tube and the inner tube (hereinafter, referred to as an annular portion) and a space inside the inner tube, which are separated from each other.
  • the annular portion is filled with a reforming catalyst capable of reforming kerosene.
  • a reforming catalyst capable of reforming kerosene.
  • a water steam reforming catalyst or an autothermal reforming catalyst a catalyst having steam reforming ability and partial oxidation reforming ability
  • a known catalytic force capable of steam reforming or autothermal reforming of kerosene to be used can be appropriately selected and employed.
  • the reforming catalyst includes a reforming catalyst having kerosene oxidation activity.
  • Kerosene oxidation activity means the ability to generate heat by oxidizing kerosene with oxygen on the catalyst.
  • a panner is connected to one end of the inner tube.
  • a panner can be attached to the inner tube itself.
  • the inner pipe and the burner may be arranged apart from each other and connected between them by a conduit to guide the burner combustion gas to the inner pipe.
  • one perner may be connected to the inner pipe of each double pipe, but the combustion gas of one parner may be branched and supplied to multiple inner pipes. ,.
  • the panner is appropriately selected from known panners capable of combusting the panner fuel to be used. It can be done.
  • kerosene used as a reforming raw material is preferable to use as the fuel for the PANA. This is because it is not necessary to prepare a separate fuel. However, other fuels can be used.
  • SOFC various shapes such as a flat plate shape and a cylindrical shape can be appropriately selected and employed.
  • SOFC may be a single cell! /, But for practical use, a stack in which a plurality of single cells are arranged is preferably used. In this case, there may be one or more stacks.
  • SOFC, reformer and panner can be accommodated in a container such as a can and modularized.
  • the reformer is arranged at a position where direct heat transfer to the outer surface of the SOFC force outer tube is possible. It is preferred that substantially no shielding be placed between the reformer and the SOFC. In addition, it is preferable to shorten the distance between the reformer and the SOFC as much as possible. For example, multiple double tubes can be placed around the SOFC stack.
  • the reforming catalyst can receive the exhaust heat of SOFC from the outer pipe surface, and can receive the heat of the Pana combustion gas flowing in the inner pipe. It becomes.
  • the heat supply to the reformer is insufficient with only the exhaust heat of the fuel cell due to disturbance or a rapid increase in the reforming amount, combustion may be performed with the PANANER, and the heat shortage may be compensated by the heat of the PANANA combustion gas. Therefore, the solid oxide fuel cell can be stably operated without reducing the efficiency.
  • the heat required for reforming can be provided with only SOFC exhaust heat, the burner does not have to be burned.
  • the necessity of Pana combustion can be judged by the reforming catalyst outlet temperature.
  • the reforming catalyst outlet temperature is preferably 580 ° C or higher, more preferably 620 ° C or higher, and further preferably 650 ° C or higher.
  • the temperature is preferably 850 ° C or lower, more preferably 800 ° C or lower, and further preferably 750 ° C or lower.
  • FIG. 1 is a schematic diagram showing an embodiment of the internal reforming SOFC of the present invention.
  • the reformer 1 has an outer pipe la and an inner pipe lb, and a panner 4 is connected to the inner pipe. With outer tube A reforming catalyst 5 is filled in the annular portion between the inner pipe and the inner pipe. The reformer and SOFC3 are placed close to each other and there is a gap between them (no shield is placed).
  • the reformer and the SOFC are accommodated in a container 6.
  • the panner is provided through the wall of the container.
  • the temperature of the reformer catalyst can be continuously monitored and ONZOFF control can be performed so that the temperature becomes a predetermined value or higher.
  • Each supply gas is appropriately preheated as necessary and then supplied to the reformer or SOFC.
  • the indirect internal reforming SOFC of the present invention can be used for, for example, a stationary or mobile power generation system, and a cogeneration system.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fuel Cell (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne une pile à combustible à oxyde solide à reformage interne indirect utilisant du kérosène comme matériau brut de reformage, qui même lorsque les conditions de fonctionnement varient, peut fonctionner de manière stable sans dégradation de l'efficacité. Ladite pile à combustible à oxyde solide à reformage interne indirect comprend un reformeur permettant le reformage du kérosène, une pile à combustible à oxyde solide utilisant un gaz reformé obtenu à partir du reformeur comme combustible, et un brûleur destiné à chauffer le reformeur. Ledit reformeur comprend une structure de tuyau double constituée d'un tuyau externe et d'un tuyau interne. Un catalyseur de reformage, qui peut effectuer le reformage du kérosène par reformage à la vapeur, est placé dans un espace entre le tuyau extérieur et le tuyau intérieur. Le reformeur est connecté à une extrémité du tuyau interne, et est disposée au niveau d'une position dans laquelle la surface externe du tuyau externe reçoit un rayonnement thermique provenant de la pile à combustible à oxyde solide.
PCT/JP2006/325772 2005-12-28 2006-12-25 Pile a combustible a oxyde solide a reformage interne indirect WO2007077791A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005377239A JP5216190B2 (ja) 2005-12-28 2005-12-28 間接内部改質型固体酸化物形燃料電池
JP2005-377239 2005-12-28

Publications (1)

Publication Number Publication Date
WO2007077791A1 true WO2007077791A1 (fr) 2007-07-12

Family

ID=38228146

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/325772 WO2007077791A1 (fr) 2005-12-28 2006-12-25 Pile a combustible a oxyde solide a reformage interne indirect

Country Status (3)

Country Link
JP (1) JP5216190B2 (fr)
TW (1) TW200746537A (fr)
WO (1) WO2007077791A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010264406A (ja) * 2009-05-15 2010-11-25 Japan Pionics Co Ltd アンモニア分解筒
JP2012238537A (ja) * 2011-05-13 2012-12-06 Honda Motor Co Ltd 燃料電池モジュール
JP2015015094A (ja) * 2013-07-03 2015-01-22 株式会社デンソー 燃料電池装置
US9640819B2 (en) 2011-05-13 2017-05-02 Honda Motor Co., Ltd. Fuel cell system

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009266541A (ja) * 2008-04-24 2009-11-12 Nippon Oil Corp 間接内部改質型固体酸化物形燃料電池システムの運転方法
TWI506846B (zh) * 2014-04-09 2015-11-01 Inst Nuclear Energy Res Atomic Energy Council 緻密型固態氧化物燃料電池發電系統

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JP2003327411A (ja) * 2002-05-10 2003-11-19 Yokohama Tlo Co Ltd 燃料電池の燃料改質装置及び燃料改質方法
JP2004288434A (ja) * 2003-03-20 2004-10-14 Nippon Oil Corp 水素製造装置および燃料電池システム
JP2005108753A (ja) * 2003-10-01 2005-04-21 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池用灯油燃料気化方法及び装置
JP2005213133A (ja) * 2004-02-02 2005-08-11 Nippon Oil Corp 改質器および燃料電池システム

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JPH07272741A (ja) * 1994-03-31 1995-10-20 Mitsubishi Heavy Ind Ltd 円筒型固体電解質型燃料電池のモジュール構造
JP2000247601A (ja) * 1999-02-24 2000-09-12 Sanyo Electric Co Ltd 燃料改質器
JP3813391B2 (ja) * 1999-09-27 2006-08-23 株式会社東芝 固体高分子型燃料電池発電装置及びその運転方法
JP2002124289A (ja) * 2000-10-19 2002-04-26 Hitachi Metals Ltd 固体電解質型燃料電池システム
JP2003007321A (ja) * 2001-04-03 2003-01-10 Masaru Ichikawa 燃料電池ハイブリッド低級炭化水素直接改質複合システム
JP3727899B2 (ja) * 2002-04-22 2005-12-21 三菱重工業株式会社 燃料電池モジュール
JP2005263618A (ja) * 2004-02-16 2005-09-29 Fuji Electric Holdings Co Ltd 燃料改質器
JP2005285593A (ja) * 2004-03-30 2005-10-13 Fuji Electric Holdings Co Ltd 燃料電池発電装置の運転方法
JP4706190B2 (ja) * 2004-05-13 2011-06-22 三菱マテリアル株式会社 固体酸化物形燃料電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003327411A (ja) * 2002-05-10 2003-11-19 Yokohama Tlo Co Ltd 燃料電池の燃料改質装置及び燃料改質方法
JP2004288434A (ja) * 2003-03-20 2004-10-14 Nippon Oil Corp 水素製造装置および燃料電池システム
JP2005108753A (ja) * 2003-10-01 2005-04-21 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池用灯油燃料気化方法及び装置
JP2005213133A (ja) * 2004-02-02 2005-08-11 Nippon Oil Corp 改質器および燃料電池システム

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010264406A (ja) * 2009-05-15 2010-11-25 Japan Pionics Co Ltd アンモニア分解筒
JP2012238537A (ja) * 2011-05-13 2012-12-06 Honda Motor Co Ltd 燃料電池モジュール
US20140080021A1 (en) * 2011-05-13 2014-03-20 Honda Motor Co., Ltd. Fuel cell module
US9362575B2 (en) 2011-05-13 2016-06-07 Honda Motor Co., Ltd. Fuel cell module
US9640819B2 (en) 2011-05-13 2017-05-02 Honda Motor Co., Ltd. Fuel cell system
JP2015015094A (ja) * 2013-07-03 2015-01-22 株式会社デンソー 燃料電池装置

Also Published As

Publication number Publication date
TW200746537A (en) 2007-12-16
JP5216190B2 (ja) 2013-06-19
JP2007179885A (ja) 2007-07-12

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