WO2013146149A1 - Module de pile à combustible - Google Patents

Module de pile à combustible Download PDF

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Publication number
WO2013146149A1
WO2013146149A1 PCT/JP2013/056167 JP2013056167W WO2013146149A1 WO 2013146149 A1 WO2013146149 A1 WO 2013146149A1 JP 2013056167 W JP2013056167 W JP 2013056167W WO 2013146149 A1 WO2013146149 A1 WO 2013146149A1
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WO
WIPO (PCT)
Prior art keywords
desulfurizer
hydrogen
fuel cell
reformer
cell module
Prior art date
Application number
PCT/JP2013/056167
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English (en)
Japanese (ja)
Inventor
俊幸 海野
修平 咲間
Original Assignee
Ｊｘ日鉱日石エネルギー株式会社
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 Ｊｘ日鉱日石エネルギー株式会社 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Publication of WO2013146149A1 publication Critical patent/WO2013146149A1/fr

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    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • H01M8/2475—Enclosures, casings or containers of fuel cell stacks
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • 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 fuel cell module.
  • a reformer that generates a reformed gas using a hydrogen-containing fuel, a cell stack that generates power using the reformed gas, and a casing that houses at least the reformer and the cell stack And a desulfurizer that desulfurizes the hydrogen-containing fuel supplied to the reformer is known.
  • Patent Document 1 describes a fuel cell module that uses a desulfurizer isolated from a casing without heating.
  • a desulfurization catalyst of this desulfurizer for example, a zeolite desulfurization catalyst supporting metal fine particles Etc. are used.
  • Patent Document 2 describes a fuel cell module that is used by heating a desulfurizer with the heat of exhaust gas from a cell stack.
  • the desulfurization catalyst may be limited to a relatively expensive one such as a zeolite desulfurization catalyst, or the overall energy efficiency may be reduced due to a decrease in exhaust gas temperature. Therefore, in recent fuel cell modules, with increasing spread to homes and the like, it is strongly required to realize cost reduction while maintaining energy efficiency.
  • an object of one aspect of the present invention is to provide a fuel cell module capable of realizing cost reduction while maintaining energy efficiency.
  • a fuel cell module includes a reformer that generates a reformed gas using a hydrogen-containing fuel, a cell stack that generates power using the reformed gas, and a modification. And a desulfurizer that desulfurizes the hydrogen-containing fuel supplied to the reformer, and the desulfurizer is thermally connected to the outer surface of the housing. Is attached.
  • the desulfurizer since the desulfurizer is attached so as to be thermally connected to the outer surface of the casing, the desulfurizer is not heated by the heat of the exhaust gas.
  • the desulfurizer can be heated by transferring heat from the cell stack, which has only been released from the body to the outside, from the casing to the desulfurizer. Therefore, it is possible to suppress a decrease in energy efficiency due to heating of the desulfurizer.
  • the desulfurizer can be heated and maintained at a high temperature in this way, it is possible to use a relatively inexpensive metal-based desulfurization catalyst that requires heating as the desulfurization catalyst. Therefore, according to one aspect of the present invention, cost reduction can be realized while maintaining energy efficiency.
  • the desulfurizer may be attached to the outer surface of the housing via a heat insulating material.
  • the heat transfer from the housing to the desulfurizer can be controlled by the heat insulating material, and as a result, the temperature of the desulfurizer can be controlled.
  • the casing and the desulfurizer may be wrapped with a heat insulating material.
  • the above effect that is, the effect of heating the desulfurizer by transferring heat from the heat generated by the cell stack from the casing to the desulfurizer instead of heating the desulfurizer with the heat of the exhaust gas, is effective. Can be demonstrated.
  • the desulfurizer has a flow path through which the hydrogen-containing fuel is circulated, and the flow path can exchange heat with each other between the inlet side through which the hydrogen-containing fuel flows and the outlet side through which the hydrogen-containing fuel flows out. It may be folded back. In this case, the temperature distribution of the desulfurizer can be made uniform, and the hydrogen-containing fuel can be suitably desulfurized.
  • FIG. 1 is a schematic block diagram showing a fuel cell module according to an embodiment of the present invention.
  • the fuel cell module 1 of this embodiment includes a housing 6 that houses at least a reformer 2, a cell stack 3, a combustion unit 4, and a water vaporizer 5.
  • the fuel cell module 1 generates power in the cell stack 3 using a hydrogen-containing fuel and an oxidant.
  • the type of the cell stack 3 in the fuel cell module 1 is not particularly limited, and examples thereof include a polymer electrolyte fuel cell (PEFC), a solid oxide fuel cell (SOFC), and a phosphoric acid type.
  • PEFC polymer electrolyte fuel cell
  • SOFC solid oxide fuel cell
  • phosphoric acid type a phosphoric acid type.
  • hydrocarbon fuel a compound containing carbon and hydrogen in the molecule (may contain other elements such as oxygen) or a mixture thereof is used.
  • hydrocarbon fuels include hydrocarbons, alcohols, ethers, and biofuels. These hydrocarbon fuels are derived from conventional fossil fuels such as petroleum and coal, and synthetic systems such as synthesis gas. Those derived from fuel and those derived from biomass can be used as appropriate. Specific examples of hydrocarbons include methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, town gas, gasoline, naphtha, kerosene, and light oil.
  • methanol and ethanol are mentioned as alcohols.
  • ethers include dimethyl ether.
  • biofuels include biogas, bioethanol, biodiesel, and biojet.
  • oxygen-enriched air is used as the oxidizing agent.
  • the reformer 2 generates a reformed gas as a hydrogen rich gas (hydrogen containing gas) from the supplied hydrogen containing fuel.
  • the reformer 2 reforms the hydrogen-containing fuel and generates a reformed gas by a reforming reaction using a reforming catalyst.
  • the reforming method in the reformer 2 is not particularly limited, and for example, steam reforming, partial oxidation reforming, autothermal reforming, and other reforming methods can be employed.
  • the reformer 2 may have a configuration for adjusting the properties in addition to the reformer reformed by the reforming catalyst depending on the properties of the hydrogen-rich gas required for the cell stack 3.
  • the reformer 2 is configured to remove carbon monoxide in the hydrogen-rich gas. (For example, a shift reaction part and a selective oxidation reaction part). The reformer 2 supplies the reformed gas to the cell stack 3.
  • PEFC polymer electrolyte fuel cell
  • PAFC phosphoric acid fuel cell
  • the cell stack 3 generates power using the reformed gas and oxidant from the reformer 2.
  • the cell stack 3 supplies the reformed gas and the oxidant, which have not been used for power generation, to the combustion unit 4 as off-gas.
  • the combustion unit 4 burns off gas supplied from the cell stack 3 and heats the reformer 2 and the water vaporizer 5.
  • the combustion unit 4 is located at the upper part of the cell stack 3.
  • the combustor 4 is composed of, for example, a case.
  • the reformed gas and the oxidant that have not been used for power generation are combusted in the case, and the reformer 2 and the water vaporizer 5 that are thermally connected to the case are provided. You may heat indirectly.
  • the combustion part 4 is comprised without a case, for example, burns the reformed gas and oxidant which were not used for electric power generation at the upper part of the cell stack 3, and heats the reformer 2 and the water vaporizer 5 directly. May be.
  • the exhaust gas generated by the combustion of the combustion unit 4 is exhausted outside the housing 6.
  • the water vaporizer 5 is an evaporator that heats and vaporizes supplied water to generate water vapor supplied to the reformer 2.
  • the water vaporizer 5 supplies the generated steam to the reformer 2. Heating of the water in the water vaporizer 5 can use heat generated in the fuel cell module 1 such as recovering heat of the reformer 2, heat of the combustion unit 4, or exhaust gas.
  • the water vaporizer 5 is disposed on the upper side of the combustion unit 4.
  • the housing 6 is a metal box having a rectangular parallelepiped shape, and has an internal space for accommodating at least the reformer 2, the cell stack 3, the combustion unit 4, and the water vaporizer 5.
  • the fuel cell module 1 of the present embodiment includes a desulfurizer 7.
  • the desulfurizer 7 has a long box-like outer shape, and desulfurizes the hydrogen-containing fuel supplied to the reformer 2.
  • the desulfurizer 7 has a desulfurization catalyst 7x for removing sulfur compounds contained in the hydrogen-containing fuel.
  • a desulfurization method of the desulfurizer 7 for example, a hydrodesulfurization method in which a sulfur compound is removed by reacting with hydrogen is employed.
  • the desulfurizer 7 supplies the desulfurized hydrogen-containing fuel to the reformer 2.
  • As the desulfurization catalyst 7x a metal desulfurization catalyst represented by Ni is used.
  • the desulfurizer 7 has a flow path 8 through which hydrogen-containing fuel flows.
  • the flow path 8 is filled with the desulfurization catalyst 7x.
  • the flow path 8 is folded back so that heat exchange can be performed between the inlet 8a side through which the hydrogen-containing fuel flows and the outlet 8b side through which the hydrogen-containing fuel flows out.
  • an inlet portion 8 a is provided at the lower portion of one side surface 7 a of the desulfurizer 7, and an outlet portion 8 b is provided at the upper portion of the side surface 7 a of the desulfurizer 7.
  • the inlet portion 8a side and the outlet portion 8b side in the flow path 8 are in contact with each other via a metal plate 7c extending in the longitudinal direction so as to vertically define the inside of the desulfurizer 7.
  • Such a flow path 8 extends straight from the inlet portion 8a to the vicinity of the other side surface 7b, is then folded back toward the side surface 7a so as to wrap around upward, and extends straight to the outlet portion 8b.
  • a diffusion layer 7y for diffusing the hydrogen-containing fuel is provided on each of the inlet 8a side and the outlet 8b side in the flow path 8.
  • An inlet pipe 7d for flowing hydrogen-containing fuel into the inlet section 8a is connected to the inlet section 8a, and an outlet pipe 7e for flowing hydrogen-containing fuel to the outside of the outlet section 8b is connected to the outlet section 8b.
  • the desulfurizer 7 is disposed horizontally on the upper surface (outer surface) 6a of the housing 6 via a heat insulating material 9, and is attached so as to be thermally connected to the upper surface 6a of the housing 6. Specifically, the desulfurizer 7 is placed on the upper surface 6 a of the casing 6 so as to sandwich the heat insulating material 9 between the desulfurizer 7 and the casing 6. In other words, the housing 6, the heat insulating material 9, and the desulfurizer 7 are in contact with each other and are stacked in this order from the bottom to the top.
  • the heat insulating material 9 has a plate shape having a predetermined thickness, and spreads on the upper surface 6a of the housing 6 so as to include at least the desulfurizer 7 when viewed from above. That is, the heat insulating material 9 is interposed between the desulfurizer 7 and the housing 6 so that the desulfurizer 7 and the housing 6 do not directly face each other.
  • this heat insulating material 9 by appropriately setting the predetermined thickness, the amount of heat transferred from the housing 6 to the desulfurizer 7 can be controlled, and the temperature of the desulfurizer 7 can be maintained at a predetermined temperature.
  • the thickness of the heat insulating material 9 here is set so that the desulfurizer 7 does not exceed the upper limit temperature, thereby improving safety and reliability.
  • the material and specification are not limited, A various thing can be used.
  • the casing 6 and the desulfurizer 7 that are thermally connected to each other with the heat insulating material 9 interposed therebetween are wrapped with an outer heat insulating material (heat insulating material) 10 so as to cover the outer periphery thereof.
  • the outer heat insulating material 10 surrounds the casing 6, the desulfurizer 7 and the heat insulating material 9 so as to be thermally sealed from the outside, and these are fixed and integrated with each other.
  • the outer heat insulating material 10 the material and specification are not limited similarly to the said heat insulating material 9, A various thing can be used.
  • the desulfurizer 7 is attached so as to be thermally connected to the upper surface 6 a of the housing 6. Therefore, instead of heating the desulfurizer 7 by the heat of the exhaust gas, as shown in FIG. 3, the heat generation of the cell stack 3 itself and the combustion of the combustion unit 4 that were conventionally only released from the housing 6 to the outside. Heat from the housing 6 is transferred from the housing 6 to the desulfurizer 7, and the desulfurizer 7 can be heated to 100 ° C or higher (preferably 150 ° C to 300 ° C). From the viewpoint of heating the desulfurizer 7, the cell stack 3 is preferably a solid oxide fuel cell or a molten carbonate fuel cell having a high operating temperature.
  • the desulfurizer 7 since it is not necessary to heat the desulfurizer 7 with the exhaust gas, it is possible to prevent the overall energy efficiency from being lowered due to a decrease in the exhaust gas temperature. That is, it is possible to suppress a decrease in energy efficiency due to heating of the desulfurizer 7. Further, since the desulfurizer 7 can be heated and maintained at a high temperature, a relatively inexpensive metal-based desulfurization catalyst that requires heating can be used as the desulfurization catalyst, and the zeolite desulfurization agent carrying metal fine particles is supported. It is not necessary to use a relatively expensive desulfurization catalyst represented by Therefore, according to the present embodiment, it is possible to realize cost reduction while maintaining energy efficiency.
  • the desulfurizer 7 can be integrated with the housing 6, and it is not necessary to arrange the desulfurizer 7 separately from the housing 6, so that the configuration can be made compact. Moreover, in this embodiment, the structure which directly heat-exchanges the desulfurizer 7 with waste gas is also unnecessary. In addition, since the desulfurizer 7 is not heated as much as the reformer 2, the desulfurization catalyst 7x is not limited to those that can be used in a temperature range very close to the reforming catalyst (for example, about 600 ° C.).
  • the desulfurizer 7 is attached to the upper surface 6a of the housing 6 via the heat insulating material 9 as described above, the heat insulating material 9 connects the housing 6 to the desulfurizer 7. It becomes possible to control the temperature of the desulfurizer 7 by controlling the heat transfer.
  • the desulfurizer is configured by transferring heat from the casing 6 to the desulfurizer 7 instead of the above-described effects, that is, heating the desulfurizer 7 with the heat of the exhaust gas, rather than the heat generated by the cell stack 3 or the combustion of the combustion unit 4. The effect of heating 7 can be effectively exhibited.
  • the flow path 8 of the desulfurizer 7 is folded back, and heat exchange is possible between the inlet 8a side and the outlet 8b side of the flow path 8. Therefore, in the desulfurizer 7, the hydrogen-containing fuel that has flowed into the inlet portion 8a is heated with the hydrogen-containing fuel that flows out from the outlet portion 8b.
  • the temperature distribution O1 of the desulfurizer 7 that has conventionally been low on the inlet 8a side of the flow path 8 and easily increased on the outlet 8b side is suitable for the desulfurization catalyst 7x.
  • the temperature distribution O2 can be made uniform so as to be maintained within a range (for example, 150 ° C. to 300 ° C.).
  • the cell stack 3, the combustion unit 4, the reformer 2, and the desulfurizer 7 are arranged in this order from the bottom to the top, and the desulfurizer 7 is heated. ing. Therefore, heat can be suitably transferred to the desulfurizer 7 using the property (convection) in which the heat is directed from the bottom to the top.
  • the arrangement position of the water vaporizer 5 is not limited to the above embodiment, and the water vaporizer 5 may be arranged at the bottom in the housing 6.
  • the desulfurizer 7 is attached to the upper surface 6 a of the housing 6.
  • the desulfurizer 7 may be attached to the bottom surface or the side surface of the housing 6. It is only necessary to be attached so as to be connected.
  • the direction in which the desulfurizer 7 is arranged is horizontal in the above embodiment, but may be vertical, and as shown in FIG. 5 (a), the desulfurizer 7 of FIG. May be reversed.
  • the form of the flow path 8 in the desulfurizer 7 is not limited to the above embodiment.
  • an inlet portion 8a ′ is provided substantially at the center of the side surface 7a in the desulfurizer 7, and an outlet portion 8b is provided above the side surface 7a so as to be close to the inlet portion 8a ′.
  • Such a flow path 8 extends straight from the inlet portion 8a to the vicinity of the side surface 7b in the pipe 7d, and then is folded back toward the side surface 7a so as to wrap around from above and below outside the pipe 7d. It extends toward.

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

Abstract

L'invention concerne un module de pile à combustible comprenant un reformeur qui produit du gaz reformé en utilisant un combustible contenant de l'hydrogène, un empilement de cellule qui produit de l'énergie en utilisant le gaz reformé, et un boîtier qui loge au moins le reformeur et l'empilement de cellule en son sein, un désulfuriseur qui désulfure le combustible contenant de l'hydrogène distribué au reformeur. Le désulfuriseur est monté sur le boîtier de façon à être connecté thermiquement à la surface externe de celui-ci.
PCT/JP2013/056167 2012-03-26 2013-03-06 Module de pile à combustible WO2013146149A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012069371A JP5939858B2 (ja) 2012-03-26 2012-03-26 燃料電池モジュール
JP2012-069371 2012-03-26

Publications (1)

Publication Number Publication Date
WO2013146149A1 true WO2013146149A1 (fr) 2013-10-03

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PCT/JP2013/056167 WO2013146149A1 (fr) 2012-03-26 2013-03-06 Module de pile à combustible

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WO (1) WO2013146149A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015115091A (ja) * 2013-12-09 2015-06-22 パナソニックＩｐマネジメント株式会社 固体酸化物形燃料電池システム及びその製造方法
JP6546398B2 (ja) * 2015-01-23 2019-07-17 東京瓦斯株式会社 燃料電池システム
JP6093392B2 (ja) * 2015-04-17 2017-03-08 本田技研工業株式会社 燃料電池モジュール

Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2006202581A (ja) * 2005-01-20 2006-08-03 Mitsubishi Electric Corp 燃料処理装置、前記燃料処理装置を用いた燃料処理方法、燃料処理装置を備えた燃料電池および燃料処理装置を備えた燃料電池への燃料供給方法
JP2009059657A (ja) * 2007-09-03 2009-03-19 Nippon Oil Corp 間接内部改質型固体酸化物形燃料電池
JP2009079155A (ja) * 2007-09-26 2009-04-16 Toshiba Fuel Cell Power Systems Corp 液体燃料脱硫装置及び液体燃料脱硫システム
JP2010272333A (ja) * 2009-05-21 2010-12-02 Jx Nippon Oil & Energy Corp 燃料電池システム
JP2012169046A (ja) * 2011-02-10 2012-09-06 Aisin Seiki Co Ltd 燃料電池システム用脱硫装置および燃料電池システム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008117652A (ja) * 2006-11-06 2008-05-22 Fuji Electric Holdings Co Ltd 燃料電池発電用脱硫器
JP5904828B2 (ja) * 2012-03-12 2016-04-20 アイシン精機株式会社 燃料電池装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006202581A (ja) * 2005-01-20 2006-08-03 Mitsubishi Electric Corp 燃料処理装置、前記燃料処理装置を用いた燃料処理方法、燃料処理装置を備えた燃料電池および燃料処理装置を備えた燃料電池への燃料供給方法
JP2009059657A (ja) * 2007-09-03 2009-03-19 Nippon Oil Corp 間接内部改質型固体酸化物形燃料電池
JP2009079155A (ja) * 2007-09-26 2009-04-16 Toshiba Fuel Cell Power Systems Corp 液体燃料脱硫装置及び液体燃料脱硫システム
JP2010272333A (ja) * 2009-05-21 2010-12-02 Jx Nippon Oil & Energy Corp 燃料電池システム
JP2012169046A (ja) * 2011-02-10 2012-09-06 Aisin Seiki Co Ltd 燃料電池システム用脱硫装置および燃料電池システム

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