WO2010125730A1 - Reformeur pour pile à combustible - Google Patents

Reformeur pour pile à combustible Download PDF

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Publication number
WO2010125730A1
WO2010125730A1 PCT/JP2010/001568 JP2010001568W WO2010125730A1 WO 2010125730 A1 WO2010125730 A1 WO 2010125730A1 JP 2010001568 W JP2010001568 W JP 2010001568W WO 2010125730 A1 WO2010125730 A1 WO 2010125730A1
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unit
reforming
fuel cell
vaporization
reformed
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PCT/JP2010/001568
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English (en)
Japanese (ja)
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藤生昭
門脇正天
梶田琢也
原嘉孝
西村佳展
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株式会社Ｅｎｅｏｓセルテック
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Publication of WO2010125730A1 publication Critical patent/WO2010125730A1/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
    • H01M8/06—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
    • 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
    • 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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
    • 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
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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
    • 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
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • 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
    • H01M2008/1095—Fuel cells with polymeric 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 reformer for a fuel cell that reforms raw fuel to generate a reformed gas used in a fuel cell.
  • a polymer electrolyte fuel cell has a basic structure in which a polymer electrolyte membrane, which is an electrolyte membrane, is disposed between a fuel electrode and an air electrode.
  • the fuel electrode contains hydrogen and the air electrode contains oxygen. It is a device that supplies the agent gas and generates power by the following electrochemical reaction.
  • the fuel electrode H 2 ⁇ 2H + + 2e - ⁇ (1)
  • Cathode 1 / 2O 2 + 2H + + 2e - ⁇ H 2 O ⁇ (2)
  • hydrogen used as a fuel for a polymer electrolyte fuel cell is a natural gas, a hydrocarbon gas such as naphtha, or a raw fuel gas of alcohols such as methanol and water vapor, which are relatively easily and inexpensively available.
  • the technique obtained by mixing and reforming in the reforming section is employed. Hydrogen gas obtained by reforming is supplied to the fuel electrode of the fuel cell and used for power generation.
  • FIG. 1 is a schematic diagram showing the configuration of a conventional fuel cell system.
  • raw fuel hydrocarbon gas such as natural gas or LPG
  • LPG low-density polyethylene glycol
  • sulfur components are removed from the raw fuel.
  • the raw fuel from which the sulfur component has been removed is supplied to the reforming unit 320.
  • the reforming unit 320 steam-reforms the raw fuel by passing the raw fuel through the catalyst heated by the burner 322 to generate a reformed gas.
  • the reformed gas generated by the reforming unit 320 is heat-exchanged with reformed water (steam) before being added to the raw fuel in the heat exchanging unit 340, and then supplied to the CO converting unit 350.
  • carbon monoxide is converted to hydrogen by a shift reaction. Thereby, the hydrogen concentration is increased and the CO concentration is reduced.
  • the reformed gas whose CO concentration has been reduced by the CO shifter 350 is heat-exchanged with the water vapor evaporated in the vaporizer 330 in the heat exchanger 342 and then supplied to the CO remover 360.
  • the CO concentration is further reduced by the CO oxidation reaction using the CO selective oxidation catalyst. Note that air necessary for the CO oxidation reaction is supplied to the reformed gas whose CO concentration has been reduced by the CO conversion unit 350.
  • the reformed gas whose CO concentration is further reduced by the CO removing unit 360 is supplied to the fuel electrode of the fuel cell 400 after exchanging heat with water vapor in the heat exchanging unit 344.
  • Air is supplied as an oxidant to the air electrode of the fuel cell 400, and power is generated by an electrochemical reaction between hydrogen and oxygen.
  • the steam necessary for the reforming reaction in the reforming unit 320 is generated from the reformed water supplied from the outside of the fuel cell system 300.
  • the liquid reforming water supplied from the outside is vaporized by exchanging heat with the exhaust gas from the burner 322 in the vaporizing section 330 to become water vapor.
  • the water vapor generated by the vaporization unit 330 is heat-exchanged with the reformed gas in the order of the heat exchange unit 342, the CO removal unit 360, and the heat exchange unit 344, and then the reformed gas in the order of the CO conversion unit 350 and the heat exchange unit 340. After further heat exchange, it is mixed with the desulfurized raw fuel.
  • the present invention has been made in view of these problems, and its purpose is to suppress fluctuations in the pressure of water vapor used for reforming raw fuel, improve robustness, and stability of the reforming reaction in the reforming section. It is in the provision of the technology which can aim at improvement.
  • An embodiment of the present invention is a fuel cell reformer.
  • the fuel cell reformer includes a reforming unit that reforms raw fuel by steam reforming, a CO reduction unit that reduces the CO concentration of reformed gas generated in the reforming unit, and heating of the reforming unit.
  • a heat exchange part and a vaporization part for vaporizing the reformed water that has passed through the pre-vaporization heat exchange part are provided, and water vapor generated in the vaporization part is supplied to the reforming part together with the raw fuel.
  • the reforming water that has been heated in advance by exchanging heat with the reformed gas in the pre-vaporization heat exchange section is supplied to the vaporization section.
  • the influence of the change in the amount of heat of the exhaust gas from the combustion means for heating the reforming catalyst is reduced, the vaporization point in the vaporization section is stabilized, and the robustness is improved.
  • the pre-vaporization heat exchange section may be provided in the CO reduction section.
  • the CO reduction unit may be a CO conversion unit that reduces the CO concentration of the reformed gas by a shift reaction.
  • you may further provide the pressure reduction part which pressure-reduces the pressure of the reforming water supplied to a vaporization part.
  • FIG. 2 is a schematic diagram showing the configuration of the fuel cell system 100 including the fuel cell reforming apparatus 10 according to the embodiment.
  • the fuel cell reforming apparatus 10 includes a desulfurization unit 20, a reforming unit 30, a burner 32, a CO conversion unit 60, heat exchange units 50 and 52, a CO removal unit 70, and a vaporization unit 40.
  • raw fuel hydrocarbon gas such as natural gas or LPG
  • the sulfur component acts as a catalyst poison for the catalyst contained in the reforming unit 30 and the fuel cell 12, and the reforming performance of the fuel cell reforming device 10 and the power generation performance of the fuel cell 12 are affected by sulfur poisoning. Decrease is suppressed.
  • the desulfurization unit 20 uses a so-called hydrodesulfurization method in which a raw fuel containing a sulfur component reacts with hydrogen in the presence of a catalyst to remove the sulfur component, or an adsorption method in which a sulfur component such as zeolite is adsorbed. Desulfurize the fuel.
  • Raw fuel from which sulfur components have been removed is supplied to the reforming unit 30.
  • the reforming unit 30 has a catalyst layer made of a reforming catalyst in which a metal catalyst such as ruthenium (Ru) is supported on a carrier such as alumina.
  • a metal catalyst such as ruthenium (Ru)
  • the raw fuel is steam reformed under the reforming catalyst heated by the burner 32, and a reformed gas containing about 80% of hydrogen (fuel) is generated.
  • the reaction temperature during steam reforming is, for example, in the range of about 650 ° C. to 700 ° C.
  • a part of the raw fuel is supplied to the burner 32 in order to raise the temperature of the reforming unit 30.
  • the fuel cell 12 can be stably operated, the supply of the raw fuel to the burner 32 is stopped, and the battery off gas discharged from the fuel cell 12 is supplied to the burner 32, whereby the temperature of the reforming unit 30 is increased. Is planned.
  • the exhaust gas generated by the combustion of the burner 32 is discharged from the fuel cell system 100 to the outside after exchanging heat with the reforming water in the vaporization section 40. Further, air is supplied to the burner 32 and used for combustion of the burner 32.
  • the reformed gas generated by the reforming unit 30 is supplied to the CO conversion unit 60 after exchanging heat with water vapor that has passed through the vaporization unit 40 when passing through the heat exchange unit 50.
  • the CO conversion unit 60 has a catalyst layer made of a Cu—Zn-based catalyst made of, for example, copper oxide or zinc oxide pellets.
  • carbon monoxide is converted to hydrogen by a shift reaction. Thereby, the hydrogen concentration of the reformed gas is increased and the CO concentration is reduced to 0.5% or less.
  • the CO selective oxidation reaction is performed, for example, in the range of about 70 ° C. to 180 ° C.
  • the reformed gas whose CO concentration has been reduced by the CO converting unit 60 is supplied to the CO removing unit 70 after exchanging heat with the reforming water when passing through the heat exchanging unit 52.
  • the CO removal unit 70 has, for example, a catalyst layer made of a CO selective oxidation catalyst in which Ru is supported on a carrier such as alumina. Reduced to. Note that air necessary for the CO oxidation reaction is supplied to the reformed gas whose CO concentration has been reduced by the CO conversion unit 60.
  • the reformed gas whose CO concentration is further reduced by the CO removing unit 70 is supplied to the fuel electrode of the fuel cell 12.
  • the fuel cell 12 is, for example, a solid polymer fuel cell, and is a laminate in which a plurality of membrane electrode assemblies (single cells) each having a solid polymer electrolyte membrane provided between a fuel electrode and an air electrode are laminated. Have. Air is supplied to the air electrode of the fuel cell 12 as an oxidant, and power is generated by an electrochemical reaction between hydrogen and oxygen.
  • the CO conversion unit 60 and the CO removal unit 70 are examples of a CO reduction unit that contributes to a reduction in the concentration of CO contained in the reformed gas.
  • the water vapor necessary for the reforming reaction in the reforming unit 30 is generated from the reformed water supplied from the outside of the fuel cell system 100.
  • the reformed water is generated by treating the clean water with a water treatment device (not shown) provided with a reverse osmosis membrane and an ion exchange resin.
  • the water treatment device reduces the conductivity of clean water and suppresses the mixing of organic substances.
  • the supply amount of the reforming water is appropriately controlled by adjusting the output of the reforming water supply pump 90.
  • the liquid reforming water supplied from the outside is heated to the reforming gas in the order of the heat exchange unit 52 and the CO conversion unit 60, and then supplied to the vaporization unit 40.
  • the reformed water starts to evaporate when heat is exchanged with the reformed gas in the CO shift section 60. Further, vaporization is completed by exchanging heat with the exhaust gas from the burner 32 in the vaporization section 40.
  • the water vapor evaporated in the vaporization unit 40 is supplied to the reforming unit 30 together with the raw fuel.
  • the heat exchange in the heat exchange unit 52 and the CO conversion unit 60 is an example of a “pre-vaporization heat exchange unit” that performs heat exchange with the reformed gas before vaporization of the reformed water is completed.
  • the reforming water heated in advance by exchanging heat with the reformed gas in the heat exchanging unit 52 and the CO converting unit 60 is supplied to the vaporizing unit 40. Therefore, the influence of the change in the calorific value of the exhaust gas from the burner 32 is reduced, the vaporization point in the vaporization unit 40 is stabilized, and the robustness is improved.
  • the decompression unit 80 is, for example, an orifice or a capillary.
  • the degree of dryness when the reforming water evaporates can be increased by reducing the pressure by the pressure reducing unit 80. Thereby, it is possible to stably obtain water vapor having a high dryness (100% or more) without being influenced by the amount of heat of the exhaust gas from the burner 32, and to suppress the pressure fluctuation of the water vapor.
  • the use of water vapor having a dryness of 100% or less for cooling the CO conversion unit 60 suppresses a change in the temperature of the water vapor, thereby producing an effect of stabilizing the temperature of the CO conversion unit 60.
  • the pressure and temperature of the reforming water before passing through the decompression unit 80 are, for example, 150 kPa and 20 ° C., respectively.
  • the pressure, temperature, and dryness of the reformed water that has passed through the decompression unit 80 and before being introduced into the vaporization unit 40 are, for example, 130 kPa, 106 ° C., and 99%, respectively.
  • FIG. 3 is a diagram showing a more detailed configuration of the fuel cell reforming apparatus 10.
  • the fuel cell reforming apparatus 10 includes a reforming unit 210, a heat exchanging unit 52, and a CO removing unit 70.
  • the reforming unit 210 includes a reforming unit 30 and a CO converting unit 60 that are integrated into a multi-column shape, and a burner 32.
  • the burner 32 mixes and burns the air taken in from the air intake 34 and the raw fuel (or cell off gas) taken in from the fuel intake 36.
  • the raw fuel gas or the like is burned by the burner 32, high-temperature exhaust gas (combustion exhaust gas) of 1200 to 1300 ° C. is generated.
  • a cylindrical combustion cylinder 220 that guides exhaust gas from the burner 32 upward is provided above the burner 32.
  • a reforming section (reforming reaction tower) 30 is provided outside the combustion cylinder 220.
  • An exhaust gas flow path 222 is formed between the combustion cylinder 220 and the reforming unit 30. The exhaust gas from the burner 32 is turned up above the combustion cylinder 220 and guided to the exhaust gas passage 222.
  • the exhaust gas flow path 222 is folded upward at the lower part of the reforming unit 30, passes through the outside of the reforming unit 30, and communicates with the exhaust gas chamber 226 provided at the upper part of the reforming unit 210.
  • the exhaust gas is discharged outside the reforming unit 210 through the exhaust gas chamber 226.
  • the mixed gas in which the raw fuel and the steam are mixed is supplied to the reforming unit 30 from the outside of the reforming unit 210 via the raw fuel supply path 260.
  • the reforming unit 30 is provided outside the combustion cylinder 220 via the exhaust gas passage 222.
  • the reforming unit 30 has a double structure, and includes an inner channel 232 provided with the catalyst layer 230 and an outer channel 234 provided outside the inner channel 232.
  • the lower part of the inner flow path 232 and the lower part of the outer flow path 234 are communicated, and the reformed gas generated in the inner flow path 232 passes through the outer flow path 234 and is provided in the upper part of the reforming unit 210. It is guided to the reformed gas chamber 240.
  • a CO conversion unit 60 is provided outside the reforming unit 30 and the burner 32 via a heat insulating member 250.
  • the reformed gas chamber 240 and the CO conversion unit 60 are connected by a pipe 242, and the reformed gas is supplied from the reformed gas chamber 240 to the CO conversion unit 60.
  • the CO conversion unit 60 has a double structure, and includes an inner channel 62 and an outer channel 66 provided outside the inner channel 62 and provided with a catalyst layer 64. A lower portion of the inner flow path 62 and a lower portion of the outer flow path 66 are communicated, and the reformed gas that has passed through the inner flow path 62 is guided to the outer flow path 66. The shift reaction proceeds by the catalyst layer 64 provided in the outer flow path 66, and the CO concentration of the reformed gas is reduced.
  • the reformed gas having a reduced CO concentration is sent to the outside of the reforming unit 210 and supplied to the CO removing unit 70 via the heat exchanging unit 52. Air is added to the reformed gas having a reduced CO concentration via the air intake 68 on the downstream side of the CO shift section 60.
  • the reformed water is heated by exchanging heat with the reformed gas in the heat exchanging section 52 and then decompressed by the decompression section 80.
  • the reformed water decompressed by the decompression unit 80 exchanges heat with the reformed gas passing through the CO transforming unit 60 and starts to evaporate when passing through the spiral pipe provided around the CO transforming unit 60. .
  • the reformed water heated in the CO conversion unit 60 is vaporized by exchanging heat with the exhaust gas in the vaporization unit 40 provided in the exhaust gas chamber 226, and becomes a water vapor having a dryness of 100% or more.
  • the water vapor generated in the vaporization section 40 is added to the raw fuel after heat exchange with the reformed gas in the heat exchange section 50 provided in the reformed gas chamber 240, and used for reforming the raw fuel in the reforming section 30. It is done.
  • the decompression unit 80 is used for decompressing the reformed water before heat exchange at the CO conversion unit 60, but the decompression unit 80 is modified after heat exchange at the CO conversion unit 60. You may be provided in the path
  • the temperature of the reformed water before being vaporized by the vaporization unit 40 may be increased by causing the CO removal unit 70 to exchange heat.
  • the present invention can be used in a fuel cell reforming apparatus that reforms raw fuel to generate reformed gas mainly composed of hydrogen gas.

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

Abstract

Selon l'invention, dans une unité de reformage (30), un combustible brut est reformé par vapeur et un gaz reformé est généré. De l'eau de reformage, qui est utilisée pour le reformage du combustible brut, est chauffée à l'avance et commence l'évaporation par échange de chaleur avec le gaz réformé dans une unité de transformation de CO (60) avant d'être évaporée par la chaleur d'un gaz d'échappement dans une unité d'évaporation (40). Entre temps, la pression de l'eau de reformage devant être distribuée à l'unité d'évaporation (40) est réduite au moyen d'une unité de réduction de pression (80).
PCT/JP2010/001568 2009-04-28 2010-03-05 Reformeur pour pile à combustible WO2010125730A1 (fr)

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JP2009-110057 2009-04-28
JP2009110057A JP5461880B2 (ja) 2009-04-28 2009-04-28 燃料電池用改質装置

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003157877A (ja) * 2001-09-04 2003-05-30 Toyota Motor Corp 燃料改質装置における改質原料のガス化制御
JP2003282114A (ja) * 2002-03-26 2003-10-03 Fuji Electric Co Ltd 燃料電池発電装置の停止方法
JP2004292260A (ja) * 2003-03-27 2004-10-21 Nissan Motor Co Ltd 燃料改質用触媒反応装置
JP2005213057A (ja) * 2004-01-27 2005-08-11 Nippon Oil Corp 水素製造装置および燃料電池システム
JP2005294207A (ja) * 2004-04-05 2005-10-20 Babcock Hitachi Kk 燃料電池システム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003157877A (ja) * 2001-09-04 2003-05-30 Toyota Motor Corp 燃料改質装置における改質原料のガス化制御
JP2003282114A (ja) * 2002-03-26 2003-10-03 Fuji Electric Co Ltd 燃料電池発電装置の停止方法
JP2004292260A (ja) * 2003-03-27 2004-10-21 Nissan Motor Co Ltd 燃料改質用触媒反応装置
JP2005213057A (ja) * 2004-01-27 2005-08-11 Nippon Oil Corp 水素製造装置および燃料電池システム
JP2005294207A (ja) * 2004-04-05 2005-10-20 Babcock Hitachi Kk 燃料電池システム

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JP5461880B2 (ja) 2014-04-02

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