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WO2012029322A1 - Hydrogen generation device and fuel cell system equipped with same - Google Patents

Hydrogen generation device and fuel cell system equipped with same Download PDF

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Publication number
WO2012029322A1
WO2012029322A1 PCT/JP2011/004908 JP2011004908W WO2012029322A1 WO 2012029322 A1 WO2012029322 A1 WO 2012029322A1 JP 2011004908 W JP2011004908 W JP 2011004908W WO 2012029322 A1 WO2012029322 A1 WO 2012029322A1
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Prior art keywords
carbon monoxide
temperature
hydrogen generator
air
combustion air
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PCT/JP2011/004908
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French (fr)
Japanese (ja)
Inventor
秀治 佐野
清 田口
洋 龍井
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Panasonic Corp
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Panasonic Corp
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    • 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
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    • 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
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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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
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    • 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 hydrogen generator that generates hydrogen by reacting a hydrocarbon fuel and water vapor, and a fuel cell system including the hydrogen generator, and particularly suitable for a relatively small fuel cell system for home use.
  • the present invention relates to an apparatus and a fuel cell system including the apparatus.
  • Polymer type (PEM) fuel cell systems are being developed as a suitable method for household fuel cell cogeneration systems.
  • the hydrogen of fuel is still inadequate, so city gas, LP gas, kerosene, etc.
  • a hydrogen generator for reforming fuel to generate a hydrogen-containing gas is essential for the system.
  • reforming methods use of steam reforming reaction, use of partial oxidation reaction, and autothermal method using both of them are known.
  • Many hydrogen generators using a steam reforming reaction in which hydrogen is easily obtained have been studied.
  • the hydrogen generation apparatus further includes a carbon monoxide reduction unit for reducing the carbon monoxide concentration in the fuel gas after reforming the hydrocarbon-based raw material in the reforming unit to generate the fuel gas. What is common is.
  • a shift unit having a shift catalyst for reducing carbon monoxide in the gas generated in the reforming unit by a water gas shift reaction, and a fuel gas sent from the shift unit Some have a selective oxidation section having a selective oxidation catalyst that sequentially oxidizes carbon monoxide with oxygen in air supplied separately.
  • the hydrocarbon fuel and water are introduced into the reforming section, heated to about 700 ° C. in the heating section, and the heat necessary for the reforming reaction, which is an endothermic reaction, is supplied to advance the reforming reaction. Since about 10% of CO is generated at this time, the carbon monoxide concentration is reduced at the downstream carbon monoxide reduction unit.
  • the catalyst temperature is controlled to about 200 ° C. to 300 ° C. and accompanied by an exothermic reaction, the conversion reaction proceeds to reduce the CO concentration to about 0.5% or less. Further, in the selective oxidation part, the catalyst temperature is controlled to about 100 ° C.
  • a hydrogen-containing gas having a hydrogen concentration of about 70% to 75% is obtained at the outlet of the selective oxidation unit, and this is supplied to hydrogen-using equipment such as a fuel cell.
  • FIG. 5 is a schematic diagram showing a schematic configuration of a conventional hydrogen generator described in Patent Document 1.
  • a flow path is formed concentrically around the heating unit 108 that heats the reforming unit 114, and folded portions are formed at both ends.
  • a reforming section 114 filled with a reforming catalyst, a shift conversion section 115 filled with a shift catalyst, and a selective oxidation section 116 filled with a selective oxidation catalyst are provided in order from the inside of the flow path. .
  • the hydrogen generator disclosed in Patent Document 1 includes a fuel supply path 110 that supplies fuel to the heating unit 108, a combustion air supply path 109 that supplies combustion air 108 to the heating unit 108 using a blower 122, and selective oxidation.
  • An air supply pipe 117 for causing the selective oxidation catalyst to perform an oxidation reaction upstream of the section 116 and a raw material introduction pipe 118 upstream of the reforming section 114 are provided. Then, a hydrocarbon fuel and water, which are raw materials for the steam reforming reaction, are supplied from the raw material introduction pipe 118.
  • the hydrogen generator disclosed in Patent Document 1 is provided with a reformed gas outlet 119 for discharging the generated hydrogen-containing gas downstream of the selective oxidation unit 116, and the reformed gas outlet 119 is provided.
  • a fuel cell for generating power using this gas is connected to the end of the gas.
  • a modified cooling air supply unit and a modified cooling unit for adjusting the temperature of the carbon monoxide reduction unit (a modified unit and / or a CO oxidation unit), and / or a CO oxidized cooling air supply unit and a CO oxidation cooling unit.
  • a modified cooling air supply unit and a modified cooling unit for adjusting the temperature of the carbon monoxide reduction unit (a modified unit and / or a CO oxidation unit), and / or a CO oxidized cooling air supply unit and a CO oxidation cooling unit.
  • Patent Document 3 the metamorphic portion is cooled by the metamorphic cooling air supplied from the metamorphic cooling air supply unit to the metamorphic cooling unit, and the air discharged from the metamorphic cooling unit is burned to the burner.
  • the CO oxidation portion is cooled by the CO oxidation cooling air supplied from the CO oxidation cooling air supply portion to the CO oxidation cooling portion, and is discharged from the CO oxidation cooling portion.
  • the present invention solves the above-described conventional problems, and maintains a carbon monoxide reducer at a predetermined temperature without impairing an efficient reforming reaction, and can easily control the heat balance of the hydrogen generator.
  • An object of the present invention is to provide a generation device and a fuel cell system including the same.
  • a hydrogen generator of the present invention includes a reformer that generates a reformed gas containing hydrogen using water and a raw material, and at least the heat of the reformed gas, and the reformed gas
  • a carbon monoxide reducer that generates fuel gas by reducing carbon monoxide therein, and is configured to burn at least one of the raw material and the fuel gas and air to heat the reformer.
  • a combustor a combustion air supply for supplying air to the combustor, a combustion air path connecting the combustor and the combustion air supply, and connecting the combustion air path and the combustor,
  • a cooling path disposed on an outer periphery of the carbon monoxide reducer so as to exchange heat between the carbon monoxide reducer and a part of the air supplied from the combustion air supplier.
  • the carbon monoxide reducer can be cooled by flowing combustion air through the cooling path, the temperature of the carbon monoxide reducer can be maintained at a predetermined temperature. Moreover, since the air which cooled the carbon monoxide reducer is supplied to a combustion air path and is utilized as combustion air in the combustor, heat loss can be suppressed.
  • the fuel cell system according to the present invention includes the hydrogen generator, and a fuel cell that generates power using the oxidant gas and the fuel gas supplied from the hydrogen generator.
  • the temperature of the carbon monoxide reducer can be maintained at a predetermined temperature, the heat balance of the hydrogen generator can be easily controlled, and stable operation can be continued. be able to.
  • FIG. 1 is a schematic diagram showing a schematic configuration of a hydrogen generator according to Embodiment 1 of the present invention.
  • FIG. 2 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention.
  • FIG. 3 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention.
  • FIG. 4 is a schematic diagram showing a schematic configuration of a fuel cell system according to Embodiment 4 of the present invention.
  • FIG. 5 is a schematic diagram showing a schematic configuration of a conventional hydrogen generator described in Patent Document 1. As shown in FIG.
  • the hydrogen generator according to Embodiment 1 of the present invention includes a reformer that generates reformed gas containing hydrogen by water and a raw material, and at least carbon monoxide in the reformed gas that is heated by the heat of the reformed gas.
  • a carbon monoxide reducer that generates fuel gas by reducing, a combustor configured to burn air and at least one of a raw material and a fuel gas, and to heat the reformer; Combustion air supply device that supplies air, a combustion air passage that connects the combustor and the combustion air supply device, a combustion air passage that connects the combustion device, and a carbon monoxide reducer and a combustion air supply device that supply the air
  • Combustion air supply device that supplies air, a combustion air passage that connects the combustor and the combustion air supply device, a combustion air passage that connects the combustion device, and a carbon monoxide reducer and a combustion air supply device that supply the air
  • the carbon monoxide reducer is a converter that reduces carbon monoxide in the reformed gas by a water gas shift reaction, a methanation device that reduces by a methanation reaction, and a carbon monoxide remover that reduces by an oxidation reaction. It is sufficient that at least one of the devices is provided.
  • exchanging heat means exchanging sensible heat
  • the hydrogen generator according to Embodiment 1 further includes a heat insulating material arranged so as to cover the outer periphery of the carbon monoxide reducer, and the cooling path is formed between the outer periphery of the carbon monoxide reducer and the heat insulating material. You may arrange
  • the cooling path may be arranged so as to be in contact with the outer periphery of the carbon monoxide reducer.
  • FIG. 1 is a schematic diagram showing a schematic configuration of a hydrogen generator according to Embodiment 1 of the present invention.
  • the first cylindrical body 1, the second cylindrical body 2, the third cylindrical body 3, and the housing 4 are arranged concentrically in order from the inside. ing.
  • a combustion exhaust gas flow path 5 is configured in a space between the first cylindrical body 1 and the second cylindrical body 2, and an annular first space is formed in the space between the second cylindrical body 2 and the third cylindrical body 3.
  • a gas flow path 6 is configured, and an annular second gas flow path 7 is configured in a space between the third cylindrical body 3 and the housing 4.
  • a combustor 8 a fuel supply path 10 that supplies fuel to the combustor 8, a combustion air supply path 9 that supplies combustion air, and a combustion chamber 11. Is provided.
  • the combustion chamber 11 and the combustion exhaust gas flow path 5 communicate with each other through the exhaust gas turn-up portion 12 in the vicinity of the lower part of the hydrogen generator 50. Further, the first gas flow path 6 and the second gas flow path 7 are communicated with each other via the raw material folding portion 13 in the vicinity of the lower portion of the hydrogen generator 50.
  • a raw material introduction pipe 18 is connected to the upstream side of the first gas flow path 6, and hydrocarbon fuel and water, which are raw materials for the steam reforming reaction, are supplied from the raw material introduction pipe 18.
  • hydrocarbon fuel natural gas may be used, and other hydrocarbon fuels such as LP gas may be used. These hydrocarbon-based fuels contain sulfur compounds added as odorants, but they are removed when passing through a desulfurization section (not shown) installed upstream of the raw material introduction pipe 18 and carbonized after desulfurization.
  • Hydrogen-based fuel is supplied to the raw material introduction pipe 18.
  • ion-exchanged water is used as the other raw material here.
  • a flow path defining member 20 is installed in a spiral shape, and between the second cylindrical body 2 and the third cylindrical body 3 along the flow path defining member 20.
  • a spiral space is formed.
  • the first gas flow path 6 is provided with a reformer 14 filled with a reforming catalyst.
  • a reforming catalyst a spherical catalyst in which metal ruthenium is supported on an alumina support may be used, or a nickel group catalyst, a platinum group catalyst, a platinum group catalyst such as rhodium, or the like may be used.
  • the reformer 14 is configured to receive a supply of water and raw materials and generate a hydrogen-rich reformed gas by a reforming reaction.
  • the second gas flow path 7 is provided with a shifter 15 filled with a shift catalyst and a selective oxidizer 16 filled with a selective oxidation catalyst.
  • the transformer 15 and the selective oxidizer 16 constitute a carbon monoxide reducer.
  • the transformer 15 is configured to reduce carbon monoxide in the reformed gas generated by the reformer 14 by a transformation reaction.
  • the selective oxidizer 16 is configured to further reduce the carbon monoxide in the reformed gas from which the carbon monoxide has been reduced by the transformer 15 by a selective oxidation reaction.
  • a spherical platinum-based catalyst may be used as the shift catalyst, or a copper / zinc-based catalyst mainly composed of copper may be used. Further, a ruthenium-based spherical catalyst may be used as the selective oxidation catalyst, and a platinum-based catalyst or the like can be selected according to the purpose.
  • the carbon monoxide reducer was comprised by the transformer 15 and the selective oxidizer 16, it is not limited to this.
  • the carbon monoxide reducer may be composed of at least one device among the transformer 15, the selective oxidizer 16, and the methanation device having the methanation catalyst.
  • the downstream end of the air supply pipe 17 is connected to the upstream side of the selective oxidizer 16 in the second gas flow path 7.
  • An air supply device (not shown) is connected to the upstream end of the air supply pipe 17. Thereby, oxygen (air) for causing the selective oxidizer 16 to perform an oxidation reaction with the selective oxidation catalyst can be supplied.
  • the upstream end of the air supply pipe 17 may be connected to a combustion air path 23 described later.
  • a fuel gas outlet 19 for discharging the fuel gas generated by the selective oxidizer 16 is provided on the downstream side of the selective oxidizer 16 in the second gas flow path 7.
  • a hydrogen-using device such as a fuel cell that generates power using fuel gas is connected.
  • the blower (combustion air supply device) 22 is configured to supply air to the combustor 8 through the combustion air passage 23.
  • a cooling path 24 configured to exchange heat with the transformer 15 and the selective oxidizer 16 is connected in the middle of the combustion air path 23.
  • the upstream end of the cooling path 24 is connected in the middle of the combustion air path 23.
  • the downstream end of the cooling path 24 is connected to a portion on the downstream side of the combustion air path 23 where the upstream end of the cooling path 24 is connected. That is, the cooling path 24 is formed so as to communicate with the combustor 8 through the combustion air supply path 9.
  • the middle path of the cooling path 24 is arranged along the outer periphery of the portion of the housing 4 where the transformer 15 and the selective oxidizer 16 are formed.
  • the hydrogen generator 50 according to Embodiment 1 is provided with a heat insulating material 25 so as to cover the entire hydrogen generator 50 (housing 4).
  • the cooling path 24 is disposed between the outer periphery of the portion of the casing 4 forming the transformer 15 and the selective oxidizer 16 and the heat insulating material 25, and the outer periphery of the casing 4 is Is placed in contact with.
  • the heat insulating material 25 a member obtained by molding a ceramic fiber may be used.
  • the operation of the hydrogen generator 50 according to Embodiment 1 will be described.
  • the first gas flow path 6 including the reformer 14 filled with the reforming catalyst, the shifter 15 filled with the shift catalyst, and the selective oxidizer 16 filled with the selective oxidation catalyst.
  • the second gas flow path 7 (inside the hydrogen generator 50) is filled with a raw material (here, natural gas) in order to suppress deterioration of each catalyst. This is because the activity of each catalyst may be deteriorated by receiving a history such as oxidation due to air mixing and water wetting due to condensation of residual water vapor.
  • the hydrogen generator 50 is started.
  • Combustion fuel is supplied to the combustor 8 from the fuel supply path 10.
  • the blower 22 operates, the combustion air is also supplied to the combustor 8, and the igniter (not shown) is operated to ignite the combustor 8 and the combustion in the combustion chamber 11. Be started.
  • a raw material in this case, natural gas
  • water are supplied from the raw material introduction pipe 18, and a mixed gas of natural gas and water vapor is supplied to the reformer 14 to perform a reforming reaction.
  • the selective oxidation reaction air is supplied from the air supply pipe 17 at substantially the same time, the reactions of the reformer 14, the shifter 15, and the selective oxidizer 16 are started, and fuel gas is generated. And when it can be judged that the temperature of each reaction part has reached the normal operation state, the supply of the fuel gas to the hydrogen utilizing device such as the fuel cell is started.
  • the hydrogen generator 50 in order for the hydrogen generator 50 to stably operate, it is necessary to keep the temperatures of the reformer 14, the transformer 15, the selective oxidizer 16, and the evaporator 21 at a predetermined temperature.
  • the reformer 14 that performs endothermic reaction is maintained at a predetermined temperature by heating by the combustor 8.
  • the transformer 15 and the selective oxidizer 16 generate heat due to the exothermic reaction of the catalyst. Therefore, it is necessary to remove the heat.
  • a part of the reaction heat generated in the transformer 15 and the selective oxidizer 16 is passed through the casing 4 by passing air through the cooling path 24.
  • heat exchange with air flowing through the cooling path 24 is performed.
  • a part of the reaction heat generated in the transformer 15 and the selective oxidizer 16 can be radiated to the air flowing through the cooling path 24.
  • part of the reaction heat generated in the transformer 15 and the selective oxidizer 16 is transmitted to the evaporation section 21 via the second cylindrical body 2 inside the transformer 15 and the selective oxidizer 16, and the heat of evaporation of water.
  • the temperatures of the transformer 15 and the selective oxidizer 16 can be maintained at a predetermined temperature by the two cooling configurations.
  • the air that has cooled the transformer 15 and the selective oxidizer 16 joins the combustion air path 23 and is used as combustion air in the combustor 8.
  • the hydrogen generator 50 according to the first embodiment configured as described above, a part of the air supplied from the blower 22 is made to flow through the cooling path 24 to be configured from the transformer 15 and the selective oxidizer 16.
  • the monoxide reduction device can be cooled. For this reason, it is possible to easily change the design of the cooling amounts of the transformer 15 and the selective oxidizer 16 by changing the amount of air flowing through the cooling path 24. Therefore, in the hydrogen generator 50 according to the first embodiment, the temperature of the transformer 15 and the selective oxidizer 16 can be maintained at a predetermined temperature, and the design of the heat balance configuration of the hydrogen generator can be facilitated.
  • the cooling path 24 branched from the combustion air path 23 and passing through the periphery of the transformer 15 and the selective oxidizer 16 is joined to the combustion air path 23 so that the converter 15 and the selective oxidation are combined.
  • the heat released from the transformer 15 and the selective oxidizer 16 to the cooling path 24 can be effectively used. For this reason, in 50 which concerns on this Embodiment 1, a heat loss can be suppressed.
  • the cooling path 24 is arranged so as to be in contact with the outer periphery of the casing 4 constituting the outer periphery of the transformer 15 and the selective oxidizer 16, so that the transformer 15 and the selective oxidizer are arranged.
  • the heat from 16 can be recovered more.
  • the hydrogen generator according to Embodiment 2 of the present invention includes a temperature detector that detects the temperature of the carbon monoxide reducer, a flow rate regulator that adjusts the flow rate of air flowing through the cooling path, and a temperature detector.
  • the embodiment further includes a controller configured to feedback control the flow regulator so that the temperature of the carbon monoxide reducer becomes a predetermined temperature based on the detected temperature.
  • the controller increases the flow rate of the air flowing through the cooling path when the temperature detected by the temperature detector is equal to or higher than the first predetermined temperature.
  • the flow regulator is controlled so that the temperature detected by the temperature detector is equal to or lower than a second predetermined temperature that is lower than the first predetermined temperature.
  • the flow rate regulator may be controlled so as to reduce the flow rate.
  • FIG. 2 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention.
  • the hydrogen generator 50 according to the second embodiment of the present invention has the same basic configuration as the hydrogen generator 50 according to the first embodiment, but includes a temperature detector 26 and a flow rate regulator. 27 and the controller 28 are different.
  • the temperature detector 26 may be in any form as long as it can detect the temperature of the carbon monoxide reducer.
  • the temperature of the transformer 15 is detected, and the detected temperature is supplied to the controller 28. It is configured to output.
  • a thermocouple or the like can be used as the temperature detector 26.
  • the flow regulator 27 may be in any form as long as the flow rate of air flowing through the cooling path 24 can be adjusted.
  • a flow rate regulation valve can be used as the flow rate regulator 27, for example.
  • the controller 28 may be in any form as long as it is a device that controls each device constituting the hydrogen generator 50.
  • the controller 28 includes an arithmetic processing unit exemplified by a microprocessor, a CPU, and the like, and a storage unit configured by a memory or the like that stores a program for executing each control operation. Then, in the controller 28, the arithmetic processing unit reads out a predetermined control program stored in the storage unit and executes it to perform various controls relating to the hydrogen generator 50.
  • controller 28 is not only configured as a single controller, but also configured as a controller group in which a plurality of controllers cooperate to execute control of the hydrogen generator 50. I do not care. Further, the controller 28 may be configured by a micro control, and may be configured by an MPU, a PLC (Programmable Logic Controller), a logic circuit, or the like.
  • MPU Microcontroller
  • PLC Programmable Logic Controller
  • the operation of the hydrogen generator 50 according to the second embodiment is basically the same as that of the hydrogen generator 50 according to the first embodiment, but the temperature of the carbon monoxide reducer is adjusted by the temperature detector 26. Is different based on the detected temperature.
  • the controller 28 feedback-controls the flow rate regulator 27 based on the temperature detected by the temperature detector 26 so that the temperature of the carbon monoxide reducer becomes a predetermined temperature.
  • the predetermined temperature can be arbitrarily set, and when the temperature detector 26 detects the temperature of the transformer 15, the predetermined temperature may be set between 200 ° C. and 300 ° C., For example, you may set to 250 degreeC. Further, when the temperature detector 26 is configured to detect the temperature of the selective oxidizer 16, the predetermined temperature may be set between 100 to 150 ° C., for example, set to 125 ° C. May be. Further, when a methanator filled with a methanation catalyst is provided instead of the selective oxidizer 16, the predetermined temperature can be set between 100 to 300 ° C., for example, 200 ° C. May be set.
  • the controller 28 controls the flow rate regulator 27 so as to increase the flow rate of the air flowing through the cooling path 24.
  • the flow rate regulator 27 is controlled so as to decrease the flow rate of the air flowing through the cooling path 24.
  • the controller 28 controls the flow rate regulator 27 so as to increase the flow rate of the air flowing through the cooling path 24 when the temperature detected by the temperature detector 26 is equal to or higher than the first predetermined temperature.
  • the flow rate of the air flowing through the cooling path 24 is decreased.
  • the flow regulator 26 may be controlled.
  • the first predetermined temperature and the second predetermined temperature can be arbitrarily set.
  • the first predetermined temperature may be set to 300 ° C.
  • the second predetermined temperature is set to 200 ° C. Also good.
  • the first predetermined temperature may be set to 150 ° C.
  • the second predetermined temperature is , 100 ° C. may be set.
  • the first predetermined temperature may be set to 300 ° C.
  • the second predetermined temperature The temperature may be set to 100 ° C.
  • the hydrogen generator 50 according to the second embodiment configured as described above has the same operational effects as the hydrogen generator 50 according to the first embodiment.
  • the flow rate regulator 27 adjusts the flow rate of the air flowing through the cooling path 24 based on the temperature detected by the temperature detector 26.
  • the cooling amount of the carbon reducer here, the transformer 15 and the selective oxidizer 16
  • the flow rate regulator 27 changes the amount of air flowing through the cooling path 24 to select the transformer 15.
  • the oxidizer 16 can be maintained at a predetermined temperature, and the heat balance of the hydrogen generator can be maintained.
  • the controller 28 controls the flow rate regulator 27 to be feedback controlled, so that the temperature of the carbon monoxide reducer is controlled to a predetermined temperature. It is not limited to this.
  • the controller 28 uses a table or map in which the relationship between the temperature of the carbon monoxide reducer and the flow rate of the air flowing through the cooling path 24 adjusted by the flow rate regulator 27 is set in advance through experiments or the like.
  • the adjuster 27 may be controlled.
  • Embodiment 3 The hydrogen generator according to Embodiment 3 of the present invention illustrates an aspect in which the flow rate regulator is an on-off valve that opens or closes the cooling path.
  • FIG. 3 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention.
  • the hydrogen generator 50 according to the third embodiment of the present invention has the same basic configuration as the hydrogen generator 50 according to the second embodiment. It is different in that it is composed of The controller 28 controls the on-off valve 29 according to the time for opening or closing the valve body of the on-off valve 29.
  • the hydrogen generator 50 according to the third embodiment configured as described above has the same operational effects as the hydrogen generator 50 according to the second embodiment.
  • the fuel cell system according to Embodiment 4 of the present invention includes any one of the hydrogen generators according to Embodiments 1 to 3 described above, the oxidant gas, and the fuel gas supplied from the hydrogen generator. And a fuel cell that generates electric power using a battery.
  • FIG. 4 is a schematic diagram showing a schematic configuration of a fuel cell system according to Embodiment 4 of the present invention.
  • a fuel cell system 60 includes a hydrogen generator 50, a fuel cell 51, and an oxidant gas supplier 52 according to Embodiment 1.
  • the fuel cell 51 may be a fuel cell such as a polymer electrolyte fuel cell or a phosphoric acid fuel cell. Since the configuration of the fuel cell 51 is the same as that of a general fuel cell, detailed description thereof is omitted.
  • the oxidant gas supply unit 52 may have any form as long as the oxidant gas (air) can be supplied to the cathode of the fuel cell 51.
  • a fan or a blower can be used as the oxidant gas supply unit 52.
  • the fuel cell system 60 according to the fourth embodiment configured as described above includes the hydrogen generator 50 according to the first embodiment, the same operation as the hydrogen generator 50 according to the first embodiment. There is an effect.
  • adopted it is not limited to this, The hydrogen generator 50 which concerns on Embodiment 2, or Embodiment 3 is used. A form provided with such a hydrogen generator 50 may be adopted.
  • the cooling path 24 is disposed around the transformer 15 and the selective oxidizer 16 constituting the carbon monoxide reducer. It is not limited to this. A configuration in which the cooling path 24 is disposed around at least one of the transformer 15 and the selective oxidizer 16 may be employed.
  • the hydrogen generator of the present invention and the fuel cell system including the hydrogen generator are useful in the field of fuel cells because stable operation can be maintained by maintaining the temperature of the carbon monoxide reducer at a predetermined temperature. is there.

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Abstract

This hydrogen generation device comprises: a reformer (14) which can generate a hydrogen-containing reformed gas from water and a raw material; a carbon monoxide decreasing unit which is heated with at least a heat of the reformed gas to decrease the amount of carbon monoxide in the reformed gas, thereby producing a fuel gas; a combustor (8) which is so adapted as to combust either the raw material and/or the fuel gas and air to heat the reformer (14); a combustion air supplier (22) which supplies air to the combustor (8); a combustion air passage (23) which connects the combustor (8) to the combustion air supplier (22); and a cooling passage (24) which connects the combustion air passage (23) to the combustor (8) and is so arranged on the periphery of the carbon monoxide decreasing unit as to achieve the heat exchange between the carbon monoxide decreasing unit and a part of air supplied by the combustion air suppler (22).

Description

水素生成装置及びそれを備える燃料電池システムHydrogen generator and fuel cell system including the same

　本発明は、炭化水素系燃料と水蒸気とを反応させて水素を生成する水素生成装置及びそれを備える燃料電池システムに関するものであり、特に家庭用等比較的小型の燃料電池システムに好適な水素生成装置及びそれを備える燃料電池システムに関する。 The present invention relates to a hydrogen generator that generates hydrogen by reacting a hydrocarbon fuel and water vapor, and a fuel cell system including the hydrogen generator, and particularly suitable for a relatively small fuel cell system for home use. The present invention relates to an apparatus and a fuel cell system including the apparatus.

　家庭用の燃料電池コージェネシステムに適した方式として高分子形（ＰＥＭ）燃料電池システムの開発が盛んであるが、燃料の水素はいまだインフラが不備であるため、都市ガス、ＬＰガス、灯油等の燃料を改質して水素含有ガスを生成するための水素生成装置がシステムに必須となっている。改質の方法としては水蒸気改質反応の利用、部分酸化反応の利用、それらを両方利用したオートサーマル法が知られているが、家庭用の高分子形燃料電池システムに対しては、高濃度の水素が得られやすい水蒸気改質反応を利用した水素生成装置が多く検討されている。 Polymer type (PEM) fuel cell systems are being developed as a suitable method for household fuel cell cogeneration systems. However, the hydrogen of fuel is still inadequate, so city gas, LP gas, kerosene, etc. A hydrogen generator for reforming fuel to generate a hydrogen-containing gas is essential for the system. As reforming methods, use of steam reforming reaction, use of partial oxidation reaction, and autothermal method using both of them are known. Many hydrogen generators using a steam reforming reaction in which hydrogen is easily obtained have been studied.

　水素生成装置には、炭化水素系の原料を改質部で改質して燃料ガスを生成した後、この燃料ガス中の一酸化炭素濃度を低減するための一酸化炭素低減部をさらに備えているものが一般的である。 The hydrogen generation apparatus further includes a carbon monoxide reduction unit for reducing the carbon monoxide concentration in the fuel gas after reforming the hydrocarbon-based raw material in the reforming unit to generate the fuel gas. What is common is.

　一酸化炭素低減部の一例としては、改質部で生成したガス中の一酸化炭素を水性ガスシフト反応で低減するための変成触媒を有する変成部と、この変成部から送出される燃料ガス中の一酸化炭素を、別途供給した空気中の酸素によって酸化する選択酸化触媒を有する選択酸化部とを順次備えたものがある。 As an example of the carbon monoxide reduction unit, a shift unit having a shift catalyst for reducing carbon monoxide in the gas generated in the reforming unit by a water gas shift reaction, and a fuel gas sent from the shift unit Some have a selective oxidation section having a selective oxidation catalyst that sequentially oxidizes carbon monoxide with oxygen in air supplied separately.

　改質部には炭化水素系燃料と水を導入し、加熱部で７００℃程度に加熱して吸熱反応である改質反応に必要な熱を供給して改質反応を進行させる。このときＣＯが１０％程度発生するので、下流の一酸化炭素低減部で一酸化炭素濃度を低減させる。一酸化炭素低減部では、まず変成部で、触媒温度を２００℃～３００℃程度に制御し発熱反応を伴いながら、変成反応を進行させＣＯ濃度を０．５％以下程度にまで低減する。さらに選択酸化部では１００℃～２００℃程度に触媒温度を制御し少量の空気を導入してＣＯを触媒上で発熱反応を伴いながら、酸化反応させてその濃度を１０ｐｐｍ以下程度にまで低減する。その結果、選択酸化部の出口では、水素濃度７０％～７５％程度の水素含有ガスが得られ、これが燃料電池等の水素利用機器に供給されることになる。 The hydrocarbon fuel and water are introduced into the reforming section, heated to about 700 ° C. in the heating section, and the heat necessary for the reforming reaction, which is an endothermic reaction, is supplied to advance the reforming reaction. Since about 10% of CO is generated at this time, the carbon monoxide concentration is reduced at the downstream carbon monoxide reduction unit. In the carbon monoxide reduction unit, first, in the conversion unit, the catalyst temperature is controlled to about 200 ° C. to 300 ° C. and accompanied by an exothermic reaction, the conversion reaction proceeds to reduce the CO concentration to about 0.5% or less. Further, in the selective oxidation part, the catalyst temperature is controlled to about 100 ° C. to 200 ° C., and a small amount of air is introduced to cause CO to undergo an exothermic reaction on the catalyst, thereby causing the oxidation reaction to reduce its concentration to about 10 ppm or less. As a result, a hydrogen-containing gas having a hydrogen concentration of about 70% to 75% is obtained at the outlet of the selective oxidation unit, and this is supplied to hydrogen-using equipment such as a fuel cell.

　また、燃料電池システム等に用いられる水素生成装置は、大きさがコンパクトであること、低コストであること、改質効率が高いこと、扱いやすいこと、高耐久性であること、等々の要求を最大限満たすことが重要である。これらの観点から、改質部および加熱部、一酸化炭素低減部をコンパクトに一体化した改質システムの開発が行われている。（例えば、特許文献１または特許文献２参照）。 In addition, hydrogen generators used in fuel cell systems and the like have demands such as compact size, low cost, high reforming efficiency, ease of handling, and high durability. It is important to meet as much as possible. From these viewpoints, a reforming system in which a reforming unit, a heating unit, and a carbon monoxide reduction unit are integrated in a compact manner has been developed. (For example, refer to Patent Document 1 or Patent Document 2).

　図５は、特許文献１に記載された従来の水素生成装置の概略構成を示す模式図である。図５に示すように、特許文献１に開示されている水素生成装置では、改質部１１４を加熱する加熱部１０８を中心に同心円上に流路が形成されていて、両端部で折り返し部を設けて流路を連通させ、流路の内側から順に、改質触媒を充填した改質部１１４、変成触媒を充填した変成部１１５、選択酸化触媒を充填した選択酸化部１１６が設けられている。 FIG. 5 is a schematic diagram showing a schematic configuration of a conventional hydrogen generator described in Patent Document 1. As shown in FIG. 5, in the hydrogen generator disclosed in Patent Document 1, a flow path is formed concentrically around the heating unit 108 that heats the reforming unit 114, and folded portions are formed at both ends. A reforming section 114 filled with a reforming catalyst, a shift conversion section 115 filled with a shift catalyst, and a selective oxidation section 116 filled with a selective oxidation catalyst are provided in order from the inside of the flow path. .

　また、特許文献１に開示されている水素生成装置には、加熱部１０８に燃料を供給する燃料供給路１１０と、送風機１２２によって燃焼空気を加熱部１０８供給する燃焼空気供給路１０９と、選択酸化部１１６の上流側に選択酸化触媒で酸化反応を行わせるための空気供給管１１７と、改質部１１４の上流側に原料導入管１１８と、が設けられている。そして、原料導入管１１８から水蒸気改質反応の原料である炭化水素系燃料と水とが供給される。 The hydrogen generator disclosed in Patent Document 1 includes a fuel supply path 110 that supplies fuel to the heating unit 108, a combustion air supply path 109 that supplies combustion air 108 to the heating unit 108 using a blower 122, and selective oxidation. An air supply pipe 117 for causing the selective oxidation catalyst to perform an oxidation reaction upstream of the section 116 and a raw material introduction pipe 118 upstream of the reforming section 114 are provided. Then, a hydrocarbon fuel and water, which are raw materials for the steam reforming reaction, are supplied from the raw material introduction pipe 118.

　さらに、特許文献１に開示されている水素生成装置には、選択酸化部１１６の下流側に、生成した水素含有ガスが排出される改質ガス出口１１９が設けられていて、改質ガス出口１１９の先にこのガスを利用して発電する燃料電池が接続されている。 Further, the hydrogen generator disclosed in Patent Document 1 is provided with a reformed gas outlet 119 for discharging the generated hydrogen-containing gas downstream of the selective oxidation unit 116, and the reformed gas outlet 119 is provided. A fuel cell for generating power using this gas is connected to the end of the gas.

　また、一酸化炭素低減部（変成部及び／又はＣＯ酸化部）の温度調整をするための変成冷却空気供給部と変成冷却部と、及び／又はＣＯ酸化冷却空気供給部とＣＯ酸化冷却部と、を備える水素発生装置が知られている（例えば、特許文献３参照）。特許文献３に開示されている水素発生装置では、変成冷却空気供給部から変成冷却部に供給された変成冷却空気により変成部を冷却し、変成冷却部から排出される空気をバーナに燃焼用空気を供給する燃焼空気供給部の空気吸い込み口近傍に供給することで、変成部の温度調整時に生じた熱を有効に利用することができる。また、特許文献３に開示されている水素発生装置では、ＣＯ酸化冷却空気供給部からＣＯ酸化冷却部に供給されたＣＯ酸化冷却空気によりＣＯ酸化部を冷却し、ＣＯ酸化冷却部から排出される空気をバーナに燃焼用空気を供給する燃焼空気供給部の空気吸い込み口近傍に供給することで、ＣＯ酸化部の温度調整時に生じた熱を有効に利用することができる。 Also, a modified cooling air supply unit and a modified cooling unit for adjusting the temperature of the carbon monoxide reduction unit (a modified unit and / or a CO oxidation unit), and / or a CO oxidized cooling air supply unit and a CO oxidation cooling unit. Are known (see, for example, Patent Document 3). In the hydrogen generator disclosed in Patent Document 3, the metamorphic portion is cooled by the metamorphic cooling air supplied from the metamorphic cooling air supply unit to the metamorphic cooling unit, and the air discharged from the metamorphic cooling unit is burned to the burner. By supplying to the vicinity of the air suction port of the combustion air supply unit that supplies the heat, it is possible to effectively use the heat generated when adjusting the temperature of the transformation unit. Further, in the hydrogen generator disclosed in Patent Document 3, the CO oxidation portion is cooled by the CO oxidation cooling air supplied from the CO oxidation cooling air supply portion to the CO oxidation cooling portion, and is discharged from the CO oxidation cooling portion. By supplying air to the vicinity of the air inlet of the combustion air supply unit that supplies combustion air to the burner, the heat generated during the temperature adjustment of the CO oxidation unit can be used effectively.

特開２００４－１７１８９２号公報JP 2004-171892 A 特開２００７－３３１９５１号公報JP 2007-331951 A 特開２００３－２１２５０９号公報JP 2003-212509 A

　改質に関わる各反応部を集積した、特許文献１又は特許文献２に開示されている一体型の水素生成装置においては、それぞれの反応部における吸熱・発熱分に相当する熱を反応部あるいは流路の壁面等を利用して効果的に熱交換させることによって、それぞれの部位を適切な温度に保ち水素生成装置としての機能を発揮させるとともに、外部へ放散する熱を極力小さくして改質効率を高くすることを目指した構成設計が行われている。 In the integrated hydrogen generator disclosed in Patent Document 1 or Patent Document 2 in which the respective reaction sections related to reforming are integrated, heat corresponding to the endothermic and exothermic components in each of the reaction sections is supplied to the reaction section or flow. By effectively exchanging heat using the walls of the road, etc., each part is maintained at an appropriate temperature to function as a hydrogen generator, and the heat dissipated to the outside is minimized to improve the reforming efficiency. The composition design aiming at making it high is performed.

　このような水素生成装置においては、吸熱反応を伴う改質部は改質部の改質反応に必要な熱は加熱部から供給される。一方、発熱反応を伴う一酸化炭素低減部の変成部と選択酸化部は、周囲の構造体の伝熱量を調整することにより変成部と選択酸化部の所定の温度になるよう保っている。その結果、水素生成装置全体が熱的にバランスして、各反応部を目的の温度に保つことが可能となる。 In such a hydrogen generator, heat required for the reforming reaction of the reforming unit is supplied from the heating unit to the reforming unit that involves an endothermic reaction. On the other hand, the transformation part and the selective oxidation part of the carbon monoxide reduction part accompanied by an exothermic reaction are kept at a predetermined temperature of the transformation part and the selective oxidation part by adjusting the heat transfer amount of the surrounding structure. As a result, the entire hydrogen generator is thermally balanced, and each reaction section can be maintained at a target temperature.

　しかし、水素生成装置の触媒や筐体など構成要素、原料ガス、水、空気などの入力条件の何れかが変化した場合、全体の熱バランスが崩れて水素生成装置としての機能を保てなくなることがある。水素生成装置のこれら諸条件が変化する度に、変成部と選択酸化部の周囲の構造体の伝熱量を調整するのは構造設計的に非常に手間が掛かるといった課題を有していた。 However, if any of the input conditions such as the components of the hydrogen generator, such as the catalyst and casing, source gas, water, air, etc. change, the overall heat balance will be lost and the function as a hydrogen generator will not be maintained. There is. Whenever these various conditions of the hydrogen generator change, adjusting the amount of heat transfer in the structure around the metamorphic part and the selective oxidation part has a problem in that it takes a lot of work in terms of structural design.

　また、特許文献３に開示されている水素発生装置では、変成冷却部又はＣＯ酸化冷却部から排出される高温の空気が燃焼空気供給部の空気吸い込み口近傍に供給されるため、大気中の常温の空気と高温の空気とが混在して、バーナに供給される。このため、変成部又はＣＯ酸化部の温度が変化した場合、燃焼空気供給部に供給される高温の空気の流量が変動し、バーナに供給される燃焼用空気中の高温の空気と常温の空気の割合が変動し、燃焼用空気中の酸素濃度が変動する。燃焼空気供給部が所定の流量の燃焼用空気を供給しようとしても、燃焼用空気中の酸素濃度が変動するため、バーナでの燃焼が安定しないおそれがあった。 In addition, in the hydrogen generator disclosed in Patent Document 3, high-temperature air discharged from the transformation cooling unit or the CO oxidation cooling unit is supplied to the vicinity of the air suction port of the combustion air supply unit. The hot air and hot air are mixed and supplied to the burner. For this reason, when the temperature of the transformation section or the CO oxidation section changes, the flow rate of the high-temperature air supplied to the combustion air supply section changes, and the high-temperature air and the normal-temperature air in the combustion air supplied to the burner The ratio of oxygen fluctuates, and the oxygen concentration in the combustion air fluctuates. Even if the combustion air supply unit tries to supply combustion air at a predetermined flow rate, the oxygen concentration in the combustion air fluctuates, which may cause unstable combustion in the burner.

　本発明は、前記従来の課題を解決するもので、効率的な改質反応を損なうことなく、一酸化炭素低減器を所定の温度に維持し、水素生成装置の熱バランスを容易にコントロールできる水素生成装置及びそれを備える燃料電池システムを提供することを目的とする。 The present invention solves the above-described conventional problems, and maintains a carbon monoxide reducer at a predetermined temperature without impairing an efficient reforming reaction, and can easily control the heat balance of the hydrogen generator. An object of the present invention is to provide a generation device and a fuel cell system including the same.

　前記従来の課題を解決するために、本発明の水素生成装置は、水と原料により水素含む改質ガスを生成する改質器と、少なくとも前記改質ガスの熱で加熱され、前記改質ガス中の一酸化炭素を低減して燃料ガスを生成する一酸化炭素低減器と、前記原料及び前記燃料ガスのうちの少なくとも一方と空気とを燃焼し、前記改質器を加熱するように構成されている燃焼器と、前記燃焼器に空気を供給する燃焼空気供給器と、前記燃焼器と前記燃焼空気供給器とを接続する燃焼空気経路と、前記燃焼空気経路と前記燃焼器を接続し、前記一酸化炭素低減器と前記燃焼空気供給器から供給される空気の一部とを熱交換させるように前記一酸化炭素低減器の外周に配置されている冷却経路と、を備える。 In order to solve the above-described conventional problems, a hydrogen generator of the present invention includes a reformer that generates a reformed gas containing hydrogen using water and a raw material, and at least the heat of the reformed gas, and the reformed gas A carbon monoxide reducer that generates fuel gas by reducing carbon monoxide therein, and is configured to burn at least one of the raw material and the fuel gas and air to heat the reformer. A combustor, a combustion air supply for supplying air to the combustor, a combustion air path connecting the combustor and the combustion air supply, and connecting the combustion air path and the combustor, A cooling path disposed on an outer periphery of the carbon monoxide reducer so as to exchange heat between the carbon monoxide reducer and a part of the air supplied from the combustion air supplier.

　これにより、冷却経路に燃焼用の空気を流すことによって、一酸化炭素低減器を冷却することができるため、一酸化炭素低減器の温度を所定の温度に保つようにすることができる。また、一酸化炭素低減器を冷却した空気は燃焼空気経路に供給され、燃焼器で燃焼用の空気として利用されるため、熱損失を抑制することができる。 Thus, since the carbon monoxide reducer can be cooled by flowing combustion air through the cooling path, the temperature of the carbon monoxide reducer can be maintained at a predetermined temperature. Moreover, since the air which cooled the carbon monoxide reducer is supplied to a combustion air path and is utilized as combustion air in the combustor, heat loss can be suppressed.

　また、本発明に係る燃料電池システムは、前記水素生成装置と、酸化剤ガス及び前記水素生成装置から供給される前記燃料ガスを用いて発電を行なう燃料電池と、を備える。 The fuel cell system according to the present invention includes the hydrogen generator, and a fuel cell that generates power using the oxidant gas and the fuel gas supplied from the hydrogen generator.

　本発明の水素生成装置及びそれを備える燃料電池システムによれば、一酸化炭素低減器の温度を所定の温度に維持し、水素生成装置の熱バランスを容易にコントロールでき、安定した運転が持続することができる。 According to the hydrogen generator of the present invention and the fuel cell system including the same, the temperature of the carbon monoxide reducer can be maintained at a predetermined temperature, the heat balance of the hydrogen generator can be easily controlled, and stable operation can be continued. be able to.

　本発明の上記目的、他の目的、特徴、及び利点は、添付図面参照の下、以下の好適な実施形態の詳細な説明から明らかにされる。 The above object, other objects, features, and advantages of the present invention will become apparent from the following detailed description of preferred embodiments with reference to the accompanying drawings.

図１は、本発明の実施の形態１に係る水素生成装置の概略構成を示す模式図である。FIG. 1 is a schematic diagram showing a schematic configuration of a hydrogen generator according to Embodiment 1 of the present invention. 図２は、本発明の実施の形態２に係る水素生成装置の概略構成を示す模式図である。FIG. 2 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention. 図３は、本発明の実施の形態３に係る水素生成装置の概略構成を示す模式図である。FIG. 3 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention. 図４は、本発明の実施の形態４に係る燃料電池システムの概略構成を示す模式図である。FIG. 4 is a schematic diagram showing a schematic configuration of a fuel cell system according to Embodiment 4 of the present invention. 図５は、特許文献１に記載された従来の水素生成装置の概略構成を示す模式図である。FIG. 5 is a schematic diagram showing a schematic configuration of a conventional hydrogen generator described in Patent Document 1. As shown in FIG.

　以下、本発明の実施の形態について、図面を参照しながら説明する。なお、全ての図面において、本発明を説明するために必要となる構成要素を抜粋して図示しており、その他の構成要素については図示を省略している。また、全ての図面において、同一または相当部分には同一符号を付し、重複する説明は省略する。さらに、以下の実施形態によって本発明が限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, components necessary for explaining the present invention are extracted and illustrated, and other components are not illustrated. Moreover, in all drawings, the same code | symbol is attached | subjected to the same or an equivalent part, and the overlapping description is abbreviate | omitted. Furthermore, the present invention is not limited by the following embodiments.

　（実施の形態１）
　本発明の実施の形態１に係る水素生成装置は、水と原料により水素含む改質ガスを生成する改質器と、少なくとも改質ガスの熱で加熱され、改質ガス中の一酸化炭素を低減して燃料ガスを生成する一酸化炭素低減器と、原料及び燃料ガスのうちの少なくとも一方と空気とを燃焼し、改質器を加熱するように構成されている燃焼器と、燃焼器に空気を供給する燃焼空気供給器と、燃焼器と燃焼空気供給器とを接続する燃焼空気経路と、燃焼空気経路と燃焼器を接続し、一酸化炭素低減器と燃焼空気供給器から供給される空気の一部とを熱交換させるように一酸化炭素低減器の外周に配置されている冷却経路と、を備える態様を例示するものである。 (Embodiment 1)
The hydrogen generator according to Embodiment 1 of the present invention includes a reformer that generates reformed gas containing hydrogen by water and a raw material, and at least carbon monoxide in the reformed gas that is heated by the heat of the reformed gas. A carbon monoxide reducer that generates fuel gas by reducing, a combustor configured to burn air and at least one of a raw material and a fuel gas, and to heat the reformer; Combustion air supply device that supplies air, a combustion air passage that connects the combustor and the combustion air supply device, a combustion air passage that connects the combustion device, and a carbon monoxide reducer and a combustion air supply device that supply the air The aspect provided with the cooling path arrange | positioned in the outer periphery of the carbon monoxide reducer so that heat exchange with some air may be illustrated.

　ここで、一酸化炭素低減器は、改質ガス中の一酸化炭素を、水性ガスシフト反応により低減する変成器、メタネーション反応により低減するメタネーション器、及び酸化反応により低減する一酸化炭素除去器のうちの少なくとも１の機器を備えていればよい。 Here, the carbon monoxide reducer is a converter that reduces carbon monoxide in the reformed gas by a water gas shift reaction, a methanation device that reduces by a methanation reaction, and a carbon monoxide remover that reduces by an oxidation reaction. It is sufficient that at least one of the devices is provided.

　また、熱交換させるとは、顕熱を交換させることをいう。 In addition, exchanging heat means exchanging sensible heat.

　また、本実施の形態１に係る水素生成装置では、一酸化炭素低減器の外周を覆うように配置されている断熱材をさらに備え、冷却経路は一酸化炭素低減器の外周と断熱材との間に配置されていてもよい。 The hydrogen generator according to Embodiment 1 further includes a heat insulating material arranged so as to cover the outer periphery of the carbon monoxide reducer, and the cooling path is formed between the outer periphery of the carbon monoxide reducer and the heat insulating material. You may arrange | position between.

　さらに、本実施の形態１に係る水素生成装置では、冷却経路は、一酸化炭素低減器の外周と接触するように配置されていてもよい。 Furthermore, in the hydrogen generator according to Embodiment 1, the cooling path may be arranged so as to be in contact with the outer periphery of the carbon monoxide reducer.

　以下、本実施の形態１に係る水素生成装置の一例について、図１を参照しながら詳細に説明する。 Hereinafter, an example of the hydrogen generator according to Embodiment 1 will be described in detail with reference to FIG.

　［水素生成装置の構成］
　図１は、本発明の実施の形態１に係る水素生成装置の概略構成を示す模式図である。 [Configuration of hydrogen generator]
FIG. 1 is a schematic diagram showing a schematic configuration of a hydrogen generator according to Embodiment 1 of the present invention.

　図１に示すように、本実施の形態１に係る水素生成装置５０では、内側から順に第１円筒体１、第２円筒体２、第３円筒体３、筐体４が同心円上に配置されている。そして、第１円筒体１と第２円筒体２との間の空間で燃焼排ガス流路５が構成され、第２円筒体２と第３円筒体３との間の空間で環状の第１のガス流路６が構成され、第３円筒体３と筐体４との間の空間で環状の第２のガス流路７が構成されている。また、第１円筒体１の内部空間には、燃焼器８と、燃焼器８に燃料を供給する燃料供給路１０と、燃焼空気を供給する燃焼空気供給路９と、燃焼室１１と、が設けられている。 As shown in FIG. 1, in the hydrogen generator 50 according to the first embodiment, the first cylindrical body 1, the second cylindrical body 2, the third cylindrical body 3, and the housing 4 are arranged concentrically in order from the inside. ing. A combustion exhaust gas flow path 5 is configured in a space between the first cylindrical body 1 and the second cylindrical body 2, and an annular first space is formed in the space between the second cylindrical body 2 and the third cylindrical body 3. A gas flow path 6 is configured, and an annular second gas flow path 7 is configured in a space between the third cylindrical body 3 and the housing 4. Further, in the internal space of the first cylindrical body 1, there are a combustor 8, a fuel supply path 10 that supplies fuel to the combustor 8, a combustion air supply path 9 that supplies combustion air, and a combustion chamber 11. Is provided.

　燃焼室１１と燃焼排ガス流路５は、水素生成装置５０の下部近傍で排気折り返し部１２を介して連通している。また、第１のガス流路６と第２のガス流路７は、水素生成装置５０の下部近傍で原料折り返し部１３を介して連通している。 The combustion chamber 11 and the combustion exhaust gas flow path 5 communicate with each other through the exhaust gas turn-up portion 12 in the vicinity of the lower part of the hydrogen generator 50. Further, the first gas flow path 6 and the second gas flow path 7 are communicated with each other via the raw material folding portion 13 in the vicinity of the lower portion of the hydrogen generator 50.

　第１のガス流路６の上流側には、原料導入管１８が接続されていて、原料導入管１８から水蒸気改質反応の原料である炭化水素系燃料と水とが供給される。炭化水素系燃料としては、天然ガスを用いていてもよく、ＬＰガス等他の炭化水素系燃料も用いてもよい。これら炭化水素系燃料は付臭剤として添加される硫黄化合物を含むが、それらは原料導入管１８の上流側に設置された脱硫部（図略）を通過するときに除去され、脱硫後の炭化水素系燃料が原料導入管１８に供給される。また、ここではもう一方の原料である水はイオン交換水が用いられている。 A raw material introduction pipe 18 is connected to the upstream side of the first gas flow path 6, and hydrocarbon fuel and water, which are raw materials for the steam reforming reaction, are supplied from the raw material introduction pipe 18. As the hydrocarbon fuel, natural gas may be used, and other hydrocarbon fuels such as LP gas may be used. These hydrocarbon-based fuels contain sulfur compounds added as odorants, but they are removed when passing through a desulfurization section (not shown) installed upstream of the raw material introduction pipe 18 and carbonized after desulfurization. Hydrogen-based fuel is supplied to the raw material introduction pipe 18. In addition, ion-exchanged water is used as the other raw material here.

　第１のガス流路６の上流側の空間には、流路規定部材２０がらせん状に設置されていて、流路規定部材２０に沿って第２円筒体２と第３円筒体３の間にらせん状の空間を形成している。水素生成装置が水素を生成する際は、原料導入管１８より原料としての水と天然ガスが供給されるが、らせん状空間が水の蒸発及び天然ガスとの混合部として機能する（この部分を蒸発部２１とする）。 In the space on the upstream side of the first gas flow path 6, a flow path defining member 20 is installed in a spiral shape, and between the second cylindrical body 2 and the third cylindrical body 3 along the flow path defining member 20. A spiral space is formed. When the hydrogen generator generates hydrogen, water and natural gas as raw materials are supplied from the raw material introduction pipe 18, but the spiral space functions as a mixing part of water evaporation and natural gas (this part is Evaporating part 21).

　第１のガス流路６には改質触媒を充填した改質器１４が設けられている。改質触媒は、アルミナ担体に金属ルテニウムを担持した球状の触媒を使用してもよく、ニッケル触媒、白金系触媒、ロジウム等の白金族系触媒等を用いてもよい。改質器１４は、水と原料との供給を受けて改質反応により水素リッチな改質ガスを生成するように構成されている。 The first gas flow path 6 is provided with a reformer 14 filled with a reforming catalyst. As the reforming catalyst, a spherical catalyst in which metal ruthenium is supported on an alumina support may be used, or a nickel group catalyst, a platinum group catalyst, a platinum group catalyst such as rhodium, or the like may be used. The reformer 14 is configured to receive a supply of water and raw materials and generate a hydrogen-rich reformed gas by a reforming reaction.

　第２のガス流路７には、変成触媒を充填した変成器１５と選択酸化触媒を充填した選択酸化器１６が設けられている。本実施の形態１においては、変成器１５と選択酸化器１６が一酸化炭素低減器を構成する。 The second gas flow path 7 is provided with a shifter 15 filled with a shift catalyst and a selective oxidizer 16 filled with a selective oxidation catalyst. In the first embodiment, the transformer 15 and the selective oxidizer 16 constitute a carbon monoxide reducer.

　変成器１５は、改質器１４で生成された改質ガス中の一酸化炭素を変成反応により低減するように構成されている。また、選択酸化器１６は、変成器１５で一酸化炭素が低減された改質ガス中の一酸化炭素を選択酸化反応によりさらに低減するように構成されている。 The transformer 15 is configured to reduce carbon monoxide in the reformed gas generated by the reformer 14 by a transformation reaction. The selective oxidizer 16 is configured to further reduce the carbon monoxide in the reformed gas from which the carbon monoxide has been reduced by the transformer 15 by a selective oxidation reaction.

　なお、ここでは、変成触媒には球状の白金系触媒を用いてもよく、銅を主体とした銅／亜鉛系触媒等を用いてもよい。また、選択酸化触媒として、ルテニウム系の球状触媒を用いてもよく、白金系触媒等も目的に応じて選択することが可能である。また、本実施の形態１においては、変成器１５と選択酸化器１６で一酸化炭素低減器を構成したが、これに限定されない。一酸化炭素低減器は、変成器１５、選択酸化器１６、及びメタネーション触媒を有するメタネーション器のうち、少なくとも１の機器で構成されていればよい。 Here, a spherical platinum-based catalyst may be used as the shift catalyst, or a copper / zinc-based catalyst mainly composed of copper may be used. Further, a ruthenium-based spherical catalyst may be used as the selective oxidation catalyst, and a platinum-based catalyst or the like can be selected according to the purpose. Moreover, in this Embodiment 1, although the carbon monoxide reducer was comprised by the transformer 15 and the selective oxidizer 16, it is not limited to this. The carbon monoxide reducer may be composed of at least one device among the transformer 15, the selective oxidizer 16, and the methanation device having the methanation catalyst.

　第２のガス流路７の選択酸化器１６の上流側には、空気供給管１７の下流端が接続されている。空気供給管１７の上流端には、空気供給器（図示せず）が接続されている。これにより、選択酸化器１６に選択酸化触媒で酸化反応を行わせるための酸素（空気）を供給することができる。なお、空気供給管１７の上流端は、後述する燃焼空気経路２３に接続されていてもよい。 The downstream end of the air supply pipe 17 is connected to the upstream side of the selective oxidizer 16 in the second gas flow path 7. An air supply device (not shown) is connected to the upstream end of the air supply pipe 17. Thereby, oxygen (air) for causing the selective oxidizer 16 to perform an oxidation reaction with the selective oxidation catalyst can be supplied. The upstream end of the air supply pipe 17 may be connected to a combustion air path 23 described later.

　第２のガス流路７の選択酸化器１６の下流側には、選択酸化器１６で生成された燃料ガスが排出される燃料ガス出口１９が設けられている、燃料ガス出口１９には、例えば、燃料ガスを利用して発電する燃料電池等の水素利用機器が接続されている。 A fuel gas outlet 19 for discharging the fuel gas generated by the selective oxidizer 16 is provided on the downstream side of the selective oxidizer 16 in the second gas flow path 7. A hydrogen-using device such as a fuel cell that generates power using fuel gas is connected.

　送風機（燃焼空気供給器）２２は、燃焼空気経路２３を介して燃焼器８に空気を供給するように構成されている。燃焼空気経路２３の途中には、変成器１５及び選択酸化器１６と熱交換するように構成されている冷却経路２４が接続されている。具体的には、冷却経路２４の上流端は、燃焼空気経路２３の途中に接続されている。冷却経路２４の下流端は、燃焼空気経路２３における冷却経路２４の上流端が接続されている部分よりも下流側の部分に接続されている。すなわち、冷却経路２４は、燃焼空気供給路９を介して、燃焼器８に連通するように形成されている。また、冷却経路２４の途中の経路は、筐体４の変成器１５と選択酸化器１６を形成する部分の外周に沿うように配置されている。 The blower (combustion air supply device) 22 is configured to supply air to the combustor 8 through the combustion air passage 23. A cooling path 24 configured to exchange heat with the transformer 15 and the selective oxidizer 16 is connected in the middle of the combustion air path 23. Specifically, the upstream end of the cooling path 24 is connected in the middle of the combustion air path 23. The downstream end of the cooling path 24 is connected to a portion on the downstream side of the combustion air path 23 where the upstream end of the cooling path 24 is connected. That is, the cooling path 24 is formed so as to communicate with the combustor 8 through the combustion air supply path 9. Further, the middle path of the cooling path 24 is arranged along the outer periphery of the portion of the housing 4 where the transformer 15 and the selective oxidizer 16 are formed.

　これにより、送風機２２から燃焼空気経路２３に供給された空気の一部が、冷却経路２４を通流して、変成器１５及び選択酸化器１６と熱交換して、熱交換した空気が、燃焼空気経路２３及び燃焼空気供給路９を介して、燃焼器８に供給される。 As a result, a part of the air supplied from the blower 22 to the combustion air path 23 flows through the cooling path 24 to exchange heat with the transformer 15 and the selective oxidizer 16, and the heat-exchanged air is converted into combustion air. The gas is supplied to the combustor 8 through the path 23 and the combustion air supply path 9.

　また、本実施の形態１に係る水素生成装置５０には、水素生成装置５０（筐体４）全体を覆うように断熱材２５が設けられている。なお、本実施の形態１においては、冷却経路２４を筐体４の変成器１５と選択酸化器１６を形成する部分の外周と断熱材２５との間に配置されていて、筐体４の外周と接触するように配置されている。断熱材２５としては、セラミックファイバーを成形した部材を用いてもよい。 In addition, the hydrogen generator 50 according to Embodiment 1 is provided with a heat insulating material 25 so as to cover the entire hydrogen generator 50 (housing 4). In the first embodiment, the cooling path 24 is disposed between the outer periphery of the portion of the casing 4 forming the transformer 15 and the selective oxidizer 16 and the heat insulating material 25, and the outer periphery of the casing 4 is Is placed in contact with. As the heat insulating material 25, a member obtained by molding a ceramic fiber may be used.

　［水素生成装置の動作］
　次に、本実施の形態１に係る水素生成装置５０の動作について説明する。水素生成装置５０の起動前においては、改質触媒を充填した改質器１４、変成触媒を充填した変成器１５、選択酸化触媒を充填した選択酸化器１６を含めた第１のガス流路６、第２のガス流路７（水素生成装置５０の内部）には、各触媒の劣化を抑制するために、原料（ここでは天然ガス）が充填されている。これは、各触媒は空気の混入による酸化、残留水蒸気の凝縮による水濡れ等の履歴を受けることにより活性の劣化が起こることがあるためである。 [Operation of hydrogen generator]
Next, the operation of the hydrogen generator 50 according to Embodiment 1 will be described. Before the hydrogen generator 50 is started, the first gas flow path 6 including the reformer 14 filled with the reforming catalyst, the shifter 15 filled with the shift catalyst, and the selective oxidizer 16 filled with the selective oxidation catalyst. The second gas flow path 7 (inside the hydrogen generator 50) is filled with a raw material (here, natural gas) in order to suppress deterioration of each catalyst. This is because the activity of each catalyst may be deteriorated by receiving a history such as oxidation due to air mixing and water wetting due to condensation of residual water vapor.

　この状態から水素生成装置５０の起動が開始される。燃料供給路１０から燃焼用燃料が燃焼器８に供給される。燃焼用燃料の供給と同時に、送風機２２が作動して、燃焼空気も燃焼器８に供給され、着火器（図示せず）を動作させることにより、燃焼器８に着火し燃焼室１１で燃焼が開始される。 From this state, the hydrogen generator 50 is started. Combustion fuel is supplied to the combustor 8 from the fuel supply path 10. Simultaneously with the supply of the fuel for combustion, the blower 22 operates, the combustion air is also supplied to the combustor 8, and the igniter (not shown) is operated to ignite the combustor 8 and the combustion in the combustion chamber 11. Be started.

　燃焼器８での燃焼開始とともに、燃焼熱及び燃焼排ガスの保有熱により、燃焼室１１及び燃焼排ガス流路５の温度が上昇し、隣接する第１のガス流路６及び第１のガス流路６内に設けられた改質器１４が加熱される。 With the start of combustion in the combustor 8, the temperature of the combustion chamber 11 and the combustion exhaust gas passage 5 rises due to the combustion heat and the retained heat of the combustion exhaust gas, and the adjacent first gas passage 6 and first gas passage The reformer 14 provided in 6 is heated.

　蒸発部２１が１００℃を越えた時点で、原料導入管１８から原料（ここでは、天然ガス）と水が供給され、改質器１４に天然ガスと水蒸気の混合ガスが供給されて改質反応が開始される。ほぼ同時期に空気供給管１７から選択酸化反応用空気が供給されると、改質器１４、変成器１５、選択酸化器１６の反応が開始され、燃料ガスが生成される。そして、各反応部の温度が通常運転状態に至ったと判断できた時点で、燃料電池等の水素利用機器に燃料ガスの供給が開始される。 When the evaporation section 21 exceeds 100 ° C., a raw material (in this case, natural gas) and water are supplied from the raw material introduction pipe 18, and a mixed gas of natural gas and water vapor is supplied to the reformer 14 to perform a reforming reaction. Is started. When the selective oxidation reaction air is supplied from the air supply pipe 17 at substantially the same time, the reactions of the reformer 14, the shifter 15, and the selective oxidizer 16 are started, and fuel gas is generated. And when it can be judged that the temperature of each reaction part has reached the normal operation state, the supply of the fuel gas to the hydrogen utilizing device such as the fuel cell is started.

　ところで、水素生成装置５０が安定して運転を継続するためには、改質器１４、変成器１５、選択酸化器１６、蒸発部２１の温度を所定の温度に保つ必要がある。吸熱反応する改質器１４は燃焼器８による加熱で所定の温度に保たれる。一方、変成器１５と選択酸化器１６は、触媒の発熱反応によって熱が発生するため、その熱を取り去ってやる必要がある。 Incidentally, in order for the hydrogen generator 50 to stably operate, it is necessary to keep the temperatures of the reformer 14, the transformer 15, the selective oxidizer 16, and the evaporator 21 at a predetermined temperature. The reformer 14 that performs endothermic reaction is maintained at a predetermined temperature by heating by the combustor 8. On the other hand, the transformer 15 and the selective oxidizer 16 generate heat due to the exothermic reaction of the catalyst. Therefore, it is necessary to remove the heat.

　そこで、本実施の形態１に係る水素生成装置５０では、冷却経路２４に空気を通流させることにより、変成器１５と選択酸化器１６で発生した反応熱の一部を、筐体４を介して、冷却経路２４を通流する空気と熱交換させる。これにより、変成器１５と選択酸化器１６で発生した反応熱の一部を、冷却経路２４を通流する空気に放熱することができる。また、変成器１５と選択酸化器１６で発生した反応熱の一部は、変成器１５と選択酸化器１６の内側にある第２円筒体２を介して蒸発部２１に伝わり、水の蒸発熱に利用される。 Therefore, in the hydrogen generator 50 according to Embodiment 1, a part of the reaction heat generated in the transformer 15 and the selective oxidizer 16 is passed through the casing 4 by passing air through the cooling path 24. Thus, heat exchange with air flowing through the cooling path 24 is performed. Thereby, a part of the reaction heat generated in the transformer 15 and the selective oxidizer 16 can be radiated to the air flowing through the cooling path 24. Further, part of the reaction heat generated in the transformer 15 and the selective oxidizer 16 is transmitted to the evaporation section 21 via the second cylindrical body 2 inside the transformer 15 and the selective oxidizer 16, and the heat of evaporation of water. Used for

　このように、本実施の形態１に係る水素生成装置５０では、２つの冷却構成により、変成器１５と選択酸化器１６の温度を所定の温度に保持することができる。なお、変成器１５と選択酸化器１６を冷却した空気は燃焼空気経路２３に合流し、燃焼器８で燃焼用の空気として利用する。 Thus, in the hydrogen generator 50 according to the first embodiment, the temperatures of the transformer 15 and the selective oxidizer 16 can be maintained at a predetermined temperature by the two cooling configurations. The air that has cooled the transformer 15 and the selective oxidizer 16 joins the combustion air path 23 and is used as combustion air in the combustor 8.

　このように構成された本実施の形態１に係る水素生成装置５０では、送風機２２から供給された空気の一部を冷却経路２４に通流させることにより、変成器１５と選択酸化器１６から構成される一酸化低減器を冷却することができる。このため、冷却経路２４を流れる空気量を変更することによって、変成器１５と選択酸化器１６の冷却量を容易に設計変更することが可能となる。したがって、本実施の形態１に係る水素生成装置５０では、変成器１５と選択酸化器１６の温度を所定の温度に維持し、水素生成装置の熱バランス構成の設計を容易にすることができる。 In the hydrogen generator 50 according to the first embodiment configured as described above, a part of the air supplied from the blower 22 is made to flow through the cooling path 24 to be configured from the transformer 15 and the selective oxidizer 16. The monoxide reduction device can be cooled. For this reason, it is possible to easily change the design of the cooling amounts of the transformer 15 and the selective oxidizer 16 by changing the amount of air flowing through the cooling path 24. Therefore, in the hydrogen generator 50 according to the first embodiment, the temperature of the transformer 15 and the selective oxidizer 16 can be maintained at a predetermined temperature, and the design of the heat balance configuration of the hydrogen generator can be facilitated.

　また、本実施の形態１においては、燃焼空気経路２３から分岐し変成器１５と選択酸化器１６の周囲を経由した冷却経路２４を燃焼空気経路２３に合流させることにより、変成器１５と選択酸化器１６を冷却した空気を燃焼器８で利用することで、変成器１５と選択酸化器１６から冷却経路２４に放出した熱を有効に利用できる。このため、本実施の形態１に係る５０では、熱損失を抑制することができる。 Further, in the first embodiment, the cooling path 24 branched from the combustion air path 23 and passing through the periphery of the transformer 15 and the selective oxidizer 16 is joined to the combustion air path 23 so that the converter 15 and the selective oxidation are combined. By using the air that has cooled the cooler 16 in the combustor 8, the heat released from the transformer 15 and the selective oxidizer 16 to the cooling path 24 can be effectively used. For this reason, in 50 which concerns on this Embodiment 1, a heat loss can be suppressed.

　また、本実施の形態１においては、冷却経路２４を筐体４と断熱材２５の間に設けることにより、冷却経路２４から外部への放出熱量をより抑えることができるため、熱損失をより抑制することができる。 Moreover, in this Embodiment 1, since the cooling path | route 24 is provided between the housing | casing 4 and the heat insulating material 25, since the emitted heat amount to the exterior from the cooling path | route 24 can be suppressed more, a heat loss is suppressed more. can do.

　さらに、本実施の形態１においては、冷却経路２４を変成器１５と選択酸化器１６の外周を構成する筐体４の外周と接触するように配置しているため、変成器１５と選択酸化器１６からの熱をより回収することができる。 Further, in the first embodiment, the cooling path 24 is arranged so as to be in contact with the outer periphery of the casing 4 constituting the outer periphery of the transformer 15 and the selective oxidizer 16, so that the transformer 15 and the selective oxidizer are arranged. The heat from 16 can be recovered more.

　（実施の形態２）
　本発明の実施の形態２に係る水素生成装置は、一酸化炭素低減器の温度を検出する温度検出器と、冷却経路を通流する空気の流量を調整する流量調整器と、温度検出器が検出した温度に基づいて、一酸化炭素低減器の温度が所定の温度になるように流量調整器をフィードバック制御するように構成されている制御器と、をさらに備える態様を例示するものである。 (Embodiment 2)
The hydrogen generator according to Embodiment 2 of the present invention includes a temperature detector that detects the temperature of the carbon monoxide reducer, a flow rate regulator that adjusts the flow rate of air flowing through the cooling path, and a temperature detector. The embodiment further includes a controller configured to feedback control the flow regulator so that the temperature of the carbon monoxide reducer becomes a predetermined temperature based on the detected temperature.

　また、本実施の形態２に係る水素生成装置では、制御器が、温度検出器が検出した温度が第１の所定の温度以上である場合には、冷却経路を通流する空気の流量を増加させるように流量調整器を制御し、温度検出器が検出した温度が第１の所定の温度よりも低い温度である第２の所定の温度以下である場合には、冷却経路を通流する空気の流量を減少させるように流量調整器を制御してもよい。 In the hydrogen generator according to Embodiment 2, the controller increases the flow rate of the air flowing through the cooling path when the temperature detected by the temperature detector is equal to or higher than the first predetermined temperature. The flow regulator is controlled so that the temperature detected by the temperature detector is equal to or lower than a second predetermined temperature that is lower than the first predetermined temperature. The flow rate regulator may be controlled so as to reduce the flow rate.

　以下、本実施の形態２に係る水素生成装置の一例について、図２を参照しながら詳細に説明する。 Hereinafter, an example of the hydrogen generator according to Embodiment 2 will be described in detail with reference to FIG.

　［水素生成装置の構成］
　図２は、本発明の実施の形態２に係る水素生成装置の概略構成を示す模式図である。 [Configuration of hydrogen generator]
FIG. 2 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention.

　図２に示すように、本発明の実施の形態２に係る水素生成装置５０は、実施の形態１に係る水素生成装置５０と基本的構成は同じであるが、温度検出器２６、流量調整器２７、及び制御器２８をさらに備えている点が異なる。 As shown in FIG. 2, the hydrogen generator 50 according to the second embodiment of the present invention has the same basic configuration as the hydrogen generator 50 according to the first embodiment, but includes a temperature detector 26 and a flow rate regulator. 27 and the controller 28 are different.

　温度検出器２６は、一酸化炭素低減器の温度を検出することができれば、どのような形態であってもよく、ここでは、変成器１５の温度を検出し、検出した温度を制御器２８に出力するように構成されている。温度検出器２６としては、例えば、熱電対等を使用することができる。 The temperature detector 26 may be in any form as long as it can detect the temperature of the carbon monoxide reducer. Here, the temperature of the transformer 15 is detected, and the detected temperature is supplied to the controller 28. It is configured to output. For example, a thermocouple or the like can be used as the temperature detector 26.

　流量調整器２７は、冷却経路２４を通流する空気の流量を調整することができれば、どのような形態であってもよい。流量調整器２７としては、例えば、流量調整弁を使用することができる。 The flow regulator 27 may be in any form as long as the flow rate of air flowing through the cooling path 24 can be adjusted. As the flow rate regulator 27, for example, a flow rate regulation valve can be used.

　制御器２８は、水素生成装置５０を構成する各機器を制御する機器であれば、どのような形態であってもよい。制御器２８は、マイクロプロセッサ、ＣＰＵ等に例示される演算処理部と、各制御動作を実行するためのプログラムを格納した、メモリ等から構成される記憶部と、を備えている。そして、制御器２８は、演算処理部が、記憶部に格納された所定の制御プログラムを読み出し、これを実行することにより、水素生成装置５０に関する各種の制御を行う。 The controller 28 may be in any form as long as it is a device that controls each device constituting the hydrogen generator 50. The controller 28 includes an arithmetic processing unit exemplified by a microprocessor, a CPU, and the like, and a storage unit configured by a memory or the like that stores a program for executing each control operation. Then, in the controller 28, the arithmetic processing unit reads out a predetermined control program stored in the storage unit and executes it to perform various controls relating to the hydrogen generator 50.

　なお、制御器２８は、単独の制御器で構成される形態だけでなく、複数の制御器が協働して水素生成装置５０の制御を実行する制御器群で構成される形態であっても構わない。また、制御器２８は、マイクロコントロールで構成されていてもよく、ＭＰＵ、ＰＬＣ(Ｐｒｏｇｒａｍｍａｂｌｅ　Ｌｏｇｉｃ　Ｃｏｎｔｒｏｌｌｅｒ)、論理回路等によって構成されていてもよい。 Note that the controller 28 is not only configured as a single controller, but also configured as a controller group in which a plurality of controllers cooperate to execute control of the hydrogen generator 50. I do not care. Further, the controller 28 may be configured by a micro control, and may be configured by an MPU, a PLC (Programmable Logic Controller), a logic circuit, or the like.

　［水素生成装置の動作］
　次に、本実施の形態２に係る水素生成装置５０の動作について図２を参照しながら説明する。 [Operation of hydrogen generator]
Next, the operation of the hydrogen generator 50 according to the second embodiment will be described with reference to FIG.

　本実施の形態２に係る水素生成装置５０の動作は、実施の形態１に係る水素生成装置５０と基本的に同様の動作が行われるが、一酸化炭素低減器の温度調整を温度検出器２６が検出した温度に基づいて行われる点が異なる。 The operation of the hydrogen generator 50 according to the second embodiment is basically the same as that of the hydrogen generator 50 according to the first embodiment, but the temperature of the carbon monoxide reducer is adjusted by the temperature detector 26. Is different based on the detected temperature.

　具体的には、例えば、制御器２８は、温度検出器２６が検出した温度に基づいて、一酸化炭素低減器の温度が所定の温度になるように流量調整器２７をフィードバック制御する。ここで、所定の温度は任意に設定することができ、温度検出器２６が変成器１５の温度を検出する場合には、所定の温度は、２００～３００℃の間で設定してもよく、例えば、２５０℃に設定してもよい。また、温度検出器２６が、選択酸化器１６の温度を検出するように構成されている場合には、所定の温度は１００～１５０℃の間で設定してもよく、例えば、１２５℃に設定してもよい。さらに、選択酸化器１６に代えてメタネーション触媒が充填されたメタネーション器が設けられている場合には、所定の温度は、１００～３００℃の間で設定することができ、例えば、２００℃に設定してもよい。 Specifically, for example, the controller 28 feedback-controls the flow rate regulator 27 based on the temperature detected by the temperature detector 26 so that the temperature of the carbon monoxide reducer becomes a predetermined temperature. Here, the predetermined temperature can be arbitrarily set, and when the temperature detector 26 detects the temperature of the transformer 15, the predetermined temperature may be set between 200 ° C. and 300 ° C., For example, you may set to 250 degreeC. Further, when the temperature detector 26 is configured to detect the temperature of the selective oxidizer 16, the predetermined temperature may be set between 100 to 150 ° C., for example, set to 125 ° C. May be. Further, when a methanator filled with a methanation catalyst is provided instead of the selective oxidizer 16, the predetermined temperature can be set between 100 to 300 ° C., for example, 200 ° C. May be set.

　そして、制御器２８は、温度検出器２６が検出した温度が、所定の温度よりも高い場合には、冷却経路２４を通流する空気の流量を増大させるように流量調整器２７を制御し、所定の温度よりも低い場合には、冷却経路２４を通流する空気の流量を減少させるように流量調整器２７を制御する。 When the temperature detected by the temperature detector 26 is higher than the predetermined temperature, the controller 28 controls the flow rate regulator 27 so as to increase the flow rate of the air flowing through the cooling path 24. When the temperature is lower than the predetermined temperature, the flow rate regulator 27 is controlled so as to decrease the flow rate of the air flowing through the cooling path 24.

　また、制御器２８は、温度検出器２６が検出した温度が第１の所定の温度以上である場合には、冷却経路２４を通流する空気の流量を増加させるように流量調整器２７を制御し、温度検出器２６が検出した温度が第１の所定の温度よりも低い温度である第２の所定の温度以下である場合には、冷却経路２４を通流する空気の流量を減少させるように流量調整器２６を制御してもよい。 Further, the controller 28 controls the flow rate regulator 27 so as to increase the flow rate of the air flowing through the cooling path 24 when the temperature detected by the temperature detector 26 is equal to or higher than the first predetermined temperature. When the temperature detected by the temperature detector 26 is equal to or lower than the second predetermined temperature that is lower than the first predetermined temperature, the flow rate of the air flowing through the cooling path 24 is decreased. Alternatively, the flow regulator 26 may be controlled.

　ここで、第１の所定の温度及び第２の所定の温度は、それぞれ任意に設定することができる。例えば、温度検出器２６が変成器１５の温度を検出する場合には、第１の所定の温度は、３００℃に設定してもよく、第２の所定の温度は、２００℃に設定してもよい。また、温度検出器２６が、選択酸化器１６の温度を検出するように構成されている場合には、第１の所定の温度は１５０℃に設定してもよく、第２の所定の温度は、１００℃に設定してもよい。さらに、選択酸化器１６に代えてメタネーション触媒が充填されたメタネーション器が設けられている場合には、第１の所定の温度は、３００℃に設定してもよく、第２の所定の温度は、１００℃に設定してもよい。 Here, the first predetermined temperature and the second predetermined temperature can be arbitrarily set. For example, when the temperature detector 26 detects the temperature of the transformer 15, the first predetermined temperature may be set to 300 ° C., and the second predetermined temperature is set to 200 ° C. Also good. When the temperature detector 26 is configured to detect the temperature of the selective oxidizer 16, the first predetermined temperature may be set to 150 ° C., and the second predetermined temperature is , 100 ° C. may be set. Furthermore, when a methanation device filled with a methanation catalyst is provided instead of the selective oxidizer 16, the first predetermined temperature may be set to 300 ° C., and the second predetermined temperature The temperature may be set to 100 ° C.

　このように構成された本実施の形態２に係る水素生成装置５０であっても、実施の形態１に係る水素生成装置５０と同様の作用効果を奏する。また、本実施の形態２に係る水素生成装置５０では、温度検出器２６で検出された温度に基づいて、冷却経路２４を通流する空気の流量を流量調整器２７で調整するので、一酸化炭素低減器（ここでは、変成器１５と選択酸化器１６）の冷却量を調整することができる。このため、例えば、環境温度が変化して冷却経路２４に供給される空気の温度が変化しても、流量調整器２７で冷却経路２４を流れる空気量を変化させることで、変成器１５と選択酸化器１６を所定の温度に維持することができ、水素生成装置の熱バランスを保つことができる。 Even the hydrogen generator 50 according to the second embodiment configured as described above has the same operational effects as the hydrogen generator 50 according to the first embodiment. Further, in the hydrogen generator 50 according to the second embodiment, the flow rate regulator 27 adjusts the flow rate of the air flowing through the cooling path 24 based on the temperature detected by the temperature detector 26. The cooling amount of the carbon reducer (here, the transformer 15 and the selective oxidizer 16) can be adjusted. Therefore, for example, even if the ambient temperature changes and the temperature of the air supplied to the cooling path 24 changes, the flow rate regulator 27 changes the amount of air flowing through the cooling path 24 to select the transformer 15. The oxidizer 16 can be maintained at a predetermined temperature, and the heat balance of the hydrogen generator can be maintained.

　なお、本実施の形態２に係る水素生成装置５０では、制御器２８は、流量調整器２７をフィードバック制御することにより、一酸化炭素低減器の温度を所定の温度になるように制御したが、これに限定されない。例えば、制御器２８は、一酸化炭素低減器の温度と流量調整器２７により調整する冷却経路２４を通流する空気の流量との関係を予め実験等により設定したテーブル又はマップを用いて、流量調整器２７を制御してもよい。 In the hydrogen generator 50 according to the second embodiment, the controller 28 controls the flow rate regulator 27 to be feedback controlled, so that the temperature of the carbon monoxide reducer is controlled to a predetermined temperature. It is not limited to this. For example, the controller 28 uses a table or map in which the relationship between the temperature of the carbon monoxide reducer and the flow rate of the air flowing through the cooling path 24 adjusted by the flow rate regulator 27 is set in advance through experiments or the like. The adjuster 27 may be controlled.

　（実施の形態３）
　本発明の実施の形態３に係る水素生成装置は、流量調整器が、冷却経路を開放又は閉止を行う開閉弁である態様を例示するものである。 (Embodiment 3)
The hydrogen generator according to Embodiment 3 of the present invention illustrates an aspect in which the flow rate regulator is an on-off valve that opens or closes the cooling path.

　以下、本実施の形態３に係る水素生成装置の一例について、図３を参照しながら詳細に説明する。 Hereinafter, an example of the hydrogen generator according to Embodiment 3 will be described in detail with reference to FIG.

　図３は、本発明の実施の形態３に係る水素生成装置の概略構成を示す模式図である。 FIG. 3 is a schematic diagram showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention.

　図３に示すように、本発明の実施の形態３に係る水素生成装置５０は、実施の形態２に係る水素生成装置５０と基本的構成は同じであるが、流量調整器２７が開閉弁２９で構成されている点が異なる。なお、制御器２８は、開閉弁２９の制御は、開閉弁２９の弁体を開放又は閉止する時間によって行う。 As shown in FIG. 3, the hydrogen generator 50 according to the third embodiment of the present invention has the same basic configuration as the hydrogen generator 50 according to the second embodiment. It is different in that it is composed of The controller 28 controls the on-off valve 29 according to the time for opening or closing the valve body of the on-off valve 29.

　このように構成された本実施の形態３に係る水素生成装置５０であっても、実施の形態２に係る水素生成装置５０と同様の作用効果を奏する。 Even the hydrogen generator 50 according to the third embodiment configured as described above has the same operational effects as the hydrogen generator 50 according to the second embodiment.

　（実施の形態４）
　本発明の実施の形態４に係る燃料電池システムは、上記実施の形態１乃至３に係る水素生成装置のうち、いずれかの水素生成装置と、酸化剤ガス及び水素生成装置から供給される燃料ガスを用いて発電を行なう燃料電池と、を備える態様を例示するものである。 (Embodiment 4)
The fuel cell system according to Embodiment 4 of the present invention includes any one of the hydrogen generators according to Embodiments 1 to 3 described above, the oxidant gas, and the fuel gas supplied from the hydrogen generator. And a fuel cell that generates electric power using a battery.

　以下、本実施の形態４に係る燃料電池システムの一例について、図４を参照しながら詳細に説明する。 Hereinafter, an example of the fuel cell system according to Embodiment 4 will be described in detail with reference to FIG.

　図４は、本発明の実施の形態４に係る燃料電池システムの概略構成を示す模式図である。 FIG. 4 is a schematic diagram showing a schematic configuration of a fuel cell system according to Embodiment 4 of the present invention.

　図４に示すように、本発明の実施の形態４に係る燃料電池システム６０は、実施の形態１に係る水素生成装置５０、燃料電池５１、及び酸化剤ガス供給器５２を備える。 As shown in FIG. 4, a fuel cell system 60 according to Embodiment 4 of the present invention includes a hydrogen generator 50, a fuel cell 51, and an oxidant gas supplier 52 according to Embodiment 1.

　燃料電池５１は、高分子電解質形燃料電池、リン酸形燃料電池等の各燃料電池を用いることができる。なお、燃料電池５１の構成については、一般的な燃料電池と同じであるため、その詳細な説明は省略する。 The fuel cell 51 may be a fuel cell such as a polymer electrolyte fuel cell or a phosphoric acid fuel cell. Since the configuration of the fuel cell 51 is the same as that of a general fuel cell, detailed description thereof is omitted.

　酸化剤ガス供給器５２は、燃料電池５１のカソードに酸化剤ガス（空気）を供給することができれば、どのような形態であってもよい。酸化剤ガス供給器５２としては、例えば、ファン又はブロワ等を使用することができる。 The oxidant gas supply unit 52 may have any form as long as the oxidant gas (air) can be supplied to the cathode of the fuel cell 51. As the oxidant gas supply unit 52, for example, a fan or a blower can be used.

　このように構成されている本実施の形態４に係る燃料電池システム６０では、実施の形態１に係る水素生成装置５０を備えているので、実施の形態１に係る水素生成装置５０と同様の作用効果を奏する。なお、本実施の形態４においては、実施の形態１に係る水素生成装置５０を備える形態を採用したが、これに限定されず、実施の形態２に係る水素生成装置５０又は実施の形態３に係る水素生成装置５０を備える形態を採用してもよい。 Since the fuel cell system 60 according to the fourth embodiment configured as described above includes the hydrogen generator 50 according to the first embodiment, the same operation as the hydrogen generator 50 according to the first embodiment. There is an effect. In addition, in this Embodiment 4, although the form provided with the hydrogen generator 50 which concerns on Embodiment 1 was employ | adopted, it is not limited to this, The hydrogen generator 50 which concerns on Embodiment 2, or Embodiment 3 is used. A form provided with such a hydrogen generator 50 may be adopted.

　なお、実施の形態１、実施の形態２、及び実施の形態３では、冷却経路２４を、一酸化炭素低減器を構成する変成器１５と選択酸化器１６の周囲に配設しているが、これに限定されない。冷却経路２４を変成器１５及び選択酸化器１６のうちの少なくとも一方の周囲に配設する構成を採用してもよい。 In the first embodiment, the second embodiment, and the third embodiment, the cooling path 24 is disposed around the transformer 15 and the selective oxidizer 16 constituting the carbon monoxide reducer. It is not limited to this. A configuration in which the cooling path 24 is disposed around at least one of the transformer 15 and the selective oxidizer 16 may be employed.

　上記説明から、当業者にとっては、本発明の多くの改良や他の実施形態が明らかである。したがって、上記説明は、例示としてのみ解釈されるべきであり、本発明を実行する最良の形態を当業者に教示する目的で提供されたものである。本発明の要旨を逸脱することなく、その構造及び／又は機能の詳細を実質的に変更できる。また、上記実施形態に開示されている複数の構成要素の適宜な組合せにより種々の発明を形成できる。 From the above description, many modifications and other embodiments of the present invention are apparent to persons skilled in the art. Accordingly, the foregoing description is to be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the scope of the invention. Moreover, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment.

　本発明の水素生成装置及びそれを備える燃料電池システムは、一酸化炭素低減器の温度を所定の温度に維持することで、安定した運転が持続することができるため、燃料電池の分野で有用である。 The hydrogen generator of the present invention and the fuel cell system including the hydrogen generator are useful in the field of fuel cells because stable operation can be maintained by maintaining the temperature of the carbon monoxide reducer at a predetermined temperature. is there.

　１　第１円筒体
　２　第２円筒体
　３　第３円筒体
　４　筐体
　５　燃焼排ガス流路
　６　第１のガス流路
　７　第２のガス流路
　８　燃焼器
　９　燃焼空気供給路
　１０　燃料供給路
　１１　燃焼室
　１２　排気折り返し部
　１３　原料折り返し部
　１４　改質器
　１５　変成器
　１６　選択酸化器
　１７　空気供給管
　１８　原料導入管
　１９　燃料ガス出口
　２０　流路規定部材
　２１　蒸発部
　２２　送風機
　２３　燃焼空気経路
　２４　冷却経路
　２５　断熱材
　２６　温度検出器
　２７　流量調整器
　２８　制御器
　２９　開閉弁
　５０　水素生成装置
　５１　燃料電池
　５２　酸化剤ガス供給器
　６０　燃料電池システム
　１０８　加熱部
　１０９　燃焼空気供給路
　１１０　燃料供給路
　１１４　改質部
　１１５　変成部
　１１６　選択酸化部
　１１７　空気供給管
　１１８　原料導入管
　１１９　改質ガス出口
　１２２　送風機 DESCRIPTION OF SYMBOLS 1 1st cylinder 2 2nd cylinder 3 3rd cylinder 4 Housing 5 Combustion exhaust gas flow path 6 1st gas flow path 7 2nd gas flow path 8 Combustor 9 Combustion air supply path 10 Fuel supply path 11 Combustion chamber 12 Exhaust turning part 13 Raw material turning part 14 Reformer 15 Transformer 16 Selective oxidizer 17 Air supply pipe 18 Raw material introduction pipe 19 Fuel gas outlet 20 Flow path regulating member 21 Evaporating part 22 Blower 23 Combustion air path 24 Cooling path DESCRIPTION OF SYMBOLS 25 Thermal insulation material 26 Temperature detector 27 Flow regulator 28 Controller 29 On-off valve 50 Hydrogen generator 51 Fuel cell 52 Oxidant gas supply device 60 Fuel cell system 108 Heating part 109 Combustion air supply path 110 Fuel supply path 114 Reformer 115 Transformation Section 116 Selective Oxidation Section 117 Air Supply Pipe 118 Raw Material Introduction Pipe 119 Reformed Gas Outlet 122 Blower

Claims (7)

　水と原料により水素含む改質ガスを生成する改質器と、
　少なくとも前記改質ガスの熱で加熱され、前記改質ガス中の一酸化炭素を低減して燃料ガスを生成する一酸化炭素低減器と、
　前記原料及び前記燃料ガスのうちの少なくとも一方と空気とを燃焼し、前記改質器を加熱するように構成されている燃焼器と、
　前記燃焼器に空気を供給する燃焼空気供給器と、
　前記燃焼器と前記燃焼空気供給器を接続する燃焼空気経路と、
　前記燃焼空気経路と前記燃焼器を接続し、前記一酸化炭素低減器と前記燃焼空気供給器から供給される空気の一部とを熱交換させるように前記一酸化炭素低減器の外周に配置されている冷却経路と、を備える、水素生成装置。 A reformer that generates reformed gas containing hydrogen from water and raw materials;
A carbon monoxide reducer that is heated by at least the heat of the reformed gas to reduce carbon monoxide in the reformed gas and generate fuel gas;
A combustor configured to combust air and at least one of the raw material and the fuel gas and to heat the reformer;
A combustion air supply for supplying air to the combustor;
A combustion air path connecting the combustor and the combustion air supply;
The combustion air path is connected to the combustor, and is disposed on the outer periphery of the carbon monoxide reducer so as to exchange heat between the carbon monoxide reducer and a part of the air supplied from the combustion air supplier. And a cooling path. 　前記一酸化炭素低減器の温度を検出する温度検出器と、
　前記冷却経路を通流する空気の流量を調整する流量調整器と、
　前記温度検出器が検出した温度に基づいて、前記一酸化炭素低減器の温度が所定の温度になるように前記流量調整器をフィードバック制御するように構成されている制御器と、をさらに備える、請求項１に記載の水素生成装置。 A temperature detector for detecting the temperature of the carbon monoxide reducer;
A flow regulator for adjusting the flow rate of air flowing through the cooling path;
A controller configured to feedback control the flow rate regulator such that the temperature of the carbon monoxide reducer becomes a predetermined temperature based on the temperature detected by the temperature detector; The hydrogen generator according to claim 1. 　前記一酸化炭素低減器の温度を検出する温度検出器と、
　前記冷却経路を通流する空気の流量を調整する流量調整器と、
　前記温度検出器が検出した温度が第１の所定の温度以上である場合には、前記冷却経路を通流する空気の流量を増加させるように、前記流量調整器を制御し、前記温度検出器が検出した温度が第１の所定の温度よりも低い温度である第２の所定の温度以下である場合には、前記冷却経路を通流する空気の流量を減少させるように、前記流量調整器を制御する制御器と、をさらに備える、請求項１に記載の水素生成装置。 A temperature detector for detecting the temperature of the carbon monoxide reducer;
A flow regulator for adjusting the flow rate of air flowing through the cooling path;
When the temperature detected by the temperature detector is equal to or higher than a first predetermined temperature, the flow rate controller is controlled to increase the flow rate of air flowing through the cooling path, and the temperature detector When the detected temperature is equal to or lower than a second predetermined temperature that is lower than the first predetermined temperature, the flow regulator is configured to reduce the flow rate of the air flowing through the cooling path. The hydrogen generation apparatus according to claim 1, further comprising a controller that controls. 　前記流量調整器は、前記冷却経路を開放又は閉止を行う開閉弁である、請求項２又は３に記載の水素生成装置。 The hydrogen generator according to claim 2 or 3, wherein the flow rate regulator is an on-off valve that opens or closes the cooling path. 　前記一酸化炭素低減器の外周を覆うように配置されている断熱材をさらに備え、
　前記冷却経路は、前記一酸化炭素低減器の外周と前記断熱材との間に配置されている、請求項１～４のいずれか１項に記載の水素生成装置。 Further comprising a heat insulating material arranged to cover the outer periphery of the carbon monoxide reducer,
The hydrogen generating apparatus according to any one of claims 1 to 4, wherein the cooling path is disposed between an outer periphery of the carbon monoxide reducer and the heat insulating material. 　前記冷却経路は、前記一酸化炭素低減器の外周と接触するように配置されている、請求項５に記載の水素生成装置。 The hydrogen generation apparatus according to claim 5, wherein the cooling path is disposed so as to be in contact with an outer periphery of the carbon monoxide reducer. 　請求項１～６のいずれかに記載の水素生成装置と、
　酸化剤ガス及び前記水素生成装置から供給される前記燃料ガスを用いて発電を行なう燃料電池と、を備える、燃料電池システム。 A hydrogen generator according to any one of claims 1 to 6;
A fuel cell system comprising: an oxidant gas and a fuel cell that generates electric power using the fuel gas supplied from the hydrogen generator.
PCT/JP2011/004908 2010-09-02 2011-09-01 Hydrogen generation device and fuel cell system equipped with same Ceased WO2012029322A1 (en)

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