WO2006046646A1 - 燃料改質器収納用容器および燃料改質装置 - Google Patents
燃料改質器収納用容器および燃料改質装置 Download PDFInfo
- Publication number
- WO2006046646A1 WO2006046646A1 PCT/JP2005/019790 JP2005019790W WO2006046646A1 WO 2006046646 A1 WO2006046646 A1 WO 2006046646A1 JP 2005019790 W JP2005019790 W JP 2005019790W WO 2006046646 A1 WO2006046646 A1 WO 2006046646A1
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- WIPO (PCT)
- Prior art keywords
- fuel reformer
- fuel
- gas adsorbent
- gas
- lid
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/2475—Enclosures, casings or containers of fuel cell stacks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00824—Ceramic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00835—Comprising catalytically active material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00873—Heat exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00905—Separation
- B01J2219/00921—Separation by absorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a fuel reformer storage container and a fuel reformer for constituting a fuel reformer using a fuel reformer that generates hydrogen gas from various fuel cartridges in a fuel cell system, for example. It is about.
- fuel cell systems have been reduced in size and are being considered for use as power sources for portable devices such as mobile phones, PDAs (Personal Digital Assistants), notebook computers, digital video cameras, and digital still cameras.
- portable devices such as mobile phones, PDAs (Personal Digital Assistants), notebook computers, digital video cameras, and digital still cameras.
- a fuel cell is a hydrocarbon gas such as methane or natural gas (CNG)! / ⁇ is fueled with an alcohol such as methanol or ethanol, and a fuel reformer using a fuel reformer. After reforming to other gases, power is generated by supplying this hydrogen gas to a power generation device called a power generation cell.
- CNG natural gas
- the fuel reforming by the fuel reformer here means a process of generating hydrogen gas by a catalytic reaction.
- a small amount of produced gas (mainly CO 2) other than hydrogen is usually discharged into the atmosphere.
- this steam reforming reaction is an endothermic reaction, it is heated with an external force heater or the like. It is necessary to maintain the reaction temperature. Therefore, in order to reform the fuel in the fuel reformer, for example, methanol is used as the fuel in order to prevent the steam reforming activity of the catalyst from being lowered and to maintain a high hydrogen gas concentration. If it is, a temperature of about 200 to 500 ° C is required, and if methane gas is used, a high temperature of about 300 to 800 ° C is required.
- a reforming temperature of about 400 to 600 ° C. is required.
- a cogeneration power generation system represented by a household fuel cell system
- the system itself is large, so that the outer wall of the fuel reformer storage container is doubled to form a vacuum container,
- a heat insulating material is filled between the inner and outer walls having a double structure, thereby preventing the heat inside the fuel reformer from being conducted to the outside and lowering the temperature of the fuel reformer. Therefore, when the fuel reformer is accommodated in the fuel reformer storage container, the fuel reformer may be directly joined and fixed to the inner wall of the double structure of the fuel reformer storage container. Is possible.
- fuel cell systems for portable devices are required to be reduced in size and height to be housed in portable devices.
- the conventional structure of the outer wall of the container for housing the fuel reformer is adopted for the fuel cell system for portable devices because the entire fuel cell system is complicated and enlarged. I can't. Therefore, in the case of a fuel cell system for portable equipment, when the fuel reformer storage container composed of a base body having a recess and a lid is evacuated to reform the fuel in the fuel reformer. It has been proposed to provide a fuel cell system that cuts off heat generated in the outside and reduces power generation loss.
- the fuel reformer In order to use such a fuel cell system stably and safely for a long time, the fuel reformer is housed in a fuel reformer housing container and the vacuum inside the fuel reformer housing container is sealed. It is necessary to keep it not only immediately but also for a long time thereafter. However, after sealing the inside of the fuel reformer storage container with the lid, the inner surface of the fuel reformer storage container and the fuel reformer The gas adsorbed on the surface of each part in the fuel reformer storage container, such as the surface of itself, is stored in the fuel reformer storage container with the influence of temperature during fuel reforming and the passage of time. There is a possibility that it will be released as a gas.
- the fuel reforming reaction is an endothermic reaction such as the steam reforming reaction of the chemical reaction formula (1)
- the fuel reformer in order to reform the fuel with the fuel reformer, the fuel reformer is heated with a heater or the like. It is necessary to maintain the reaction temperature at a constant temperature, but the temperature of the fuel reformer decreases as the heat generated by the fuel reformer force is conducted to the fuel reformer storage container as described above. It becomes easy to do.
- the present invention has been completed in view of the above-mentioned problems in the prior art.
- the purpose of the present invention is to reduce power generation loss, which can maintain a satisfactory degree of vacuum in the fuel reformer storage container. It is an object of the present invention to provide a fuel reformer storage container and a fuel reformer with a reduced number of fuel reformers.
- the present invention provides a substrate having a recess in which a fuel reformer that generates a reformed gas containing hydrogen gas from a fuel tank is housed, and the inside of the recess to discharge the reformed gas from the fuel reformer.
- a discharge pipe that communicates with the outside, a supply pipe that communicates the inside and outside of the recess to supply the fuel to the fuel reformer, and a lid that is joined so as to close the recess of the base
- a fuel reformer storage container comprising: a gas adsorbing material that is stored in the recess and adsorbs gas in the recess.
- the gas adsorbent is in proximity to or in contact with the fuel reformer between the fuel reformer and the inner surface defining the recess or between the fuel reformer and the lid.
- the It is characterized by being placed!
- the present invention is characterized in that a distance between the gas adsorbent and the discharge pipe is set smaller than a distance between the gas adsorbent and the supply pipe.
- the present invention further includes a lead terminal attached to the base so as to be led out from the inside of the recess, and the gas adsorbent is separated from the base within the recess. It is characterized by being fixed to.
- the gas adsorbent is formed by depositing metal powder on the surface of a metal plate, and a lead terminal for energizing the gas adsorbent is provided so as to communicate the inside of the recess with the outside. And a high resistance portion having a smaller cross-sectional area in the direction perpendicular to the energization direction than that of other portions is formed in a part of the energization portion of the metal plate.
- the present invention is characterized in that the high resistance portion is formed by providing a notch in the energization portion of the metal plate.
- the present invention is characterized in that the gas adsorbent is disposed to face the fuel reformer, and the notch is disposed to face the fuel reformer.
- the present invention is characterized in that a groove for exhausting the gas in the recess is formed in at least one of a joint portion of the base body to the lid body and a joint portion of the lid body to the base body. To do.
- At least one of a joint portion between the base body and the lid body and a joint portion between the lid body and the base body is projected over the entire circumference, and a part of the projecting portion is cut out.
- a groove is formed.
- the present invention is characterized in that the gas adsorbent is disposed along an inner surface of the groove side that defines the recess.
- the present invention is characterized in that the lid and the base are made of a metal material having a thermal conductivity of 120 W / mK or less.
- the present invention is a fuel reformer comprising the fuel reformer storage container of the present invention and a fuel reformer stored in the recess.
- the present invention is characterized in that the gas adsorbent is provided on the surface of the fuel reformer.
- the gas adsorbent and the fuel reformer are joined via a metal plate. It is characterized by.
- the present invention is characterized in that the gas adsorbent is disposed in a heat generating portion of the fuel reformer.
- the present invention is characterized in that the internal pressure of the recess is 10 2 Pa or less.
- the present invention is characterized in that the lid body and the base body are joined by displacement of a process method, a seam welder method, an electron beam method, or a laser beam method.
- FIG. 1 is a cross-sectional view showing a fuel reformer according to a first embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing a fuel reformer according to a second embodiment of the present invention.
- FIG. 3 is a cross-sectional view showing a fuel reformer according to a third embodiment of the present invention.
- FIG. 4 is a cross-sectional view showing a fuel reformer according to a fourth embodiment of the present invention.
- FIG. 5 is a cross-sectional view showing a fuel reformer according to a fifth embodiment of the present invention.
- FIG. 6 is a perspective transparent view of the fuel reformer of FIG.
- FIG. 7 is a perspective transparent view of the fuel reformer of FIG.
- FIG. 8 is a perspective view of a substrate in the fuel reformer of FIG.
- FIG. 9 is a cross-sectional view showing a fuel reformer according to a sixth embodiment of the present invention.
- FIG. 10 is a top perspective view of the fuel reformer of FIG. 9 excluding a part of the lid.
- FIG. 11 is a perspective perspective view of the lower surface side of the fuel reformer of FIG.
- FIG. 12 is an enlarged plan view showing a portion of the gas adsorbent in the fuel reformer of FIG. 9.
- FIG. 13 shows a part of the lid that shows the fuel reformer of the seventh embodiment of the present invention. It is the perspective view of the upper surface side except.
- FIG. 14 is an enlarged plan view showing a portion of the gas adsorbent in the fuel reformer of FIG.
- FIG. 15 is a cross-sectional view showing a fuel reformer according to an eighth embodiment of the present invention.
- Fig. 16 shows the connection between the supply pipe or discharge pipe and the base in the fuel reformer of Fig. 15. It is a principal part expanded sectional view.
- FIG. 17 is an enlarged cross-sectional view of a main part of a joint portion between a supply pipe or a discharge pipe and a base body in a fuel reformer according to a ninth embodiment of the present invention.
- FIG. 18 is an enlarged cross-sectional view of a main part of a joint portion between a supply pipe or a discharge pipe and a base body in a fuel reformer according to a tenth embodiment of the present invention.
- a fuel reformer storage container and a fuel reformer using the same according to an embodiment of the present invention will be described in detail below.
- FIG. 1 is a cross-sectional view showing a fuel reformer 20 according to a first embodiment of the present invention.
- the fuel reformer 20 includes a base 1, an external lead terminal 2 as a wiring for supplying power to the fuel reformer, a lid 4, a supply pipe 5a as a supply path for supplying fuel, and a reformer. It includes a discharge pipe 5b as a discharge path for discharging the quality gas, an insulating sealing material 8, a fuel reformer 9, a gas adsorbent 10, and a lead terminal 12 to which the gas adsorbent 10 is fixed.
- the insulating sealing material 8 seals and fixes the external lead terminal 2 and the lead terminal 12 in the through hole of the base 1 while insulating them.
- the base body 1, the lid body 4, the supply pipe 5a and the discharge pipe 5b constitute a fuel reformer storage container 11 for storing the fuel reformer 9.
- the fuel reformer 9 and the gas adsorbent 10 are housed in the fuel reformer housing container 11, and the concave portion of the base body 1 is hermetically sealed with the lid 4 to form the fuel reformer 20.
- Both the base body 1 and the lid body 4 in the present invention serve as containers for housing the fuel reformer 9.
- the base 1 and the lid 4 are made of, for example, stainless steel, Fe-Ni-Co alloy, Fe-based alloy such as Fe-Ni alloy, or metal material such as oxygen-free copper, aluminum oxide (A1
- Glass ceramics applicable to the substrate 1 and the lid 4 are composed of a glass component and a filler component.
- the glass component for example, SiO—B O A1
- SiO—B O —A1 O—MO system (where M represents Ca, Sr, Mg, Ba or Zn)
- SiO-Al -— ⁇ ⁇ — ⁇ ⁇ ⁇ system (where ⁇ 1 and ⁇ 2 are the same or different and Ca , Sr ⁇ Mg ⁇ Ba or Zn), SiO —BO —Al O —MO— MSO system (however, M 1
- filler components include Al 2 O, SiO, ZrO and alkaline earth metal oxides.
- the base body 1 and the lid body 4 are made of, for example, a dense acid-aluminum-aluminum sintered body having a relative density of 95% or more, it is manufactured as follows. For example, first, a sintering aid such as rare earth oxide powder or aluminum oxide powder is added to and mixed with aluminum oxide powder to prepare a raw material powder of an aluminum oxide sintered body. Next, an organic binder and a dispersion medium are added to the raw material powder, mixed and pasted, and the best is obtained by a doctor blade method, or an organic binder is added to the raw material powder, and press forming, rolling forming, etc. A green sheet having a predetermined thickness is produced.
- a sintering aid such as rare earth oxide powder or aluminum oxide powder is added to and mixed with aluminum oxide powder to prepare a raw material powder of an aluminum oxide sintered body.
- an organic binder and a dispersion medium are added to the raw material powder, mixed and pasted, and the best is obtained by a doctor blade method, or an organic
- the laminated body is fired at a firing maximum temperature of 1200 to 1500 ° C., for example, in a non-oxidizing atmosphere.
- the target ceramic substrate 1 and lid 4 are obtained.
- the base 1 and the lid 4 may be molded by a powder molding press method.
- the base 1 and the lid 4 are made of a metal material, they are formed into a predetermined shape by a cutting method, a pressing method, a MIM (Metal Injection Mold) method, or the like.
- the base 1 and the lid 4 are made of a metal material, the surface thereof is subjected to a covering coating process such as a Au or Ni plating process or a resin coating such as polyimide to prevent corrosion. It is hoped that for example, in the case of Au plating, the thickness is preferably about 0.1 to 5 / ⁇ ⁇ .
- the base body 1 and the lid body 4 as described above should be thin in order to allow the fuel reformer storage container 11 to be reduced in size and height, but the bending strength is mechanical strength.
- the strength is preferably over 200MPa!
- the external lead terminal 2 and the lead terminal 12 are preferably made of a metal having the same or similar thermal expansion coefficient as that of the base 1 and the lid 4, for example, Fe—Ni alloy, Fe—Ni—Co alloy. Although it is also powerful, it can prevent the occurrence of thermal strain against temperature changes during practical use. In addition, good sealability between the external lead terminal 2 and the base 1 and between the lead terminal 12 and the base 1 is obtained, and the bonding property is excellent. And weldability can be secured.
- the insulating sealing material 8 can also be made of a glass material such as borosilicate glass, alkali glass or lead glass as a main component, or a ceramic material such as oxyaluminum.
- the base 1 and the external lead terminal 2 and the base 1 and the lead terminal 12 are electrically insulated by the insulating sealing material 8 through the through-hole formed in 1, and the external lead terminal 2 and the lead terminal 1 2 Is sealed and fixed.
- the through-holes through which the external lead terminal 2 and the lead terminal 12 are formed in the base 1 can be electrically connected when the base 1 and the external lead terminal 2 and the base 1 and the lead terminal 12 are in contact with each other.
- the insulating sealing material 8 when the insulating sealing material 8 also has a ceramic material force such as acid aluminum, the insulating sealing material also has a cylindrical ceramic material force, for example, in the through hole of the base body 1 with the external lead terminal 2 and the lead terminal 12. 8 through Au-Ge for connection between insulating sealing material 8 and substrate 1, connection between insulating sealing material 8 and external lead terminal 2, and connection between insulating sealing material 8 and lead terminal 12 Alternatively, it can be performed with a brazing material such as Ag—Cu.
- the electrode 7 on the fuel reformer 9 and the external lead terminal 2 are electrically connected via the bonding wire 3. Further, by sealing the recess of the base body 1 using the lid 4, a fuel reformer is formed in which the fuel reformer 9 accommodated in the recess of the fuel reformer storage container 11 is hermetically sealed.
- the fuel reformer 9 housed in the fuel reformer housing container 11 of the present invention is a device for reforming fuel, and a fine flow in which a catalyst for reforming fuel is supported. Has a path or gap.
- the shape of the fuel reformer 9 varies, for example, as a micro chemical device, Applying manufacturing technology, etc., for example, by forming narrow grooves on a substrate of an inorganic material such as silicon, quartz, glass, metal, ceramics, etc. by a cutting method, an etching method, a blasting method, etc., a liquid flow
- a glass plate, a cover made of metal, etc. is used in close contact with the surface by anodic bonding, brazing, welding, etc. Things.
- it is a tube made of inorganic material such as quartz, glass, metal, ceramic, etc., and a catalyst for reforming fuel is carried on the inner surface.
- the fuel reformer 9 has a temperature control mechanism, for example, a thin film heater (not shown) or a thick film heater having a resistance layer and the like (not shown)
- the electrode 7 is formed on the surface as a terminal for supplying power to the heater.
- Such a heater is disposed in or near the gap in the flow path where the catalyst in the fuel reformer 9 is supported and performs fuel reforming. As a result, the heat generated from the heater can be efficiently used for the fuel reforming reaction.
- the lid 4 is attached to the base body 1 with its recesses covered by joining with a metal brazing material such as Au alloy, Ag alloy, A1 alloy or glass material, or by a seam weld method.
- a metal brazing material such as Au alloy, Ag alloy, A1 alloy or glass material, or by a seam weld method.
- Au-Sn brazing material is formed in a frame shape by punching using a die or the like by previously welding Au-Sn brazing material to the lid 4. After the material is placed between the base body 1 and the lid body 4, there is a sealing furnace! / ⁇ is connected to the base body 1 with a seam welder, so that the fuel reformer storage container 11 The fuel reformer 9 can be sealed inside.
- the electrode 7 on the fuel reformer 9 is electrically connected to the external lead terminal 2 provided on the base 1 through the bonding wire 3.
- the heater formed on the surface or inside of the fuel reformer 9 can be heated through the electrode 7. as a result
- the reaction temperature can be maintained in the fuel reformer 9, and the fuel reforming reaction can be stabilized.
- the supply pipe 5a and the discharge pipe 5b are a supply path for the raw material or the fuel gas fluid and a discharge path for the reformed gas containing hydrogen, respectively.
- the supply pipe 5a and the discharge pipe 5b are made of, for example, a metal material such as Fe-Ni alloy, Fe-Ni-Co alloy, stainless steel, AlO-based sintered body, 3A1
- Ceramic material such as ceramic sintered body, highly heat-resistant resin material such as polyimide, or glass.
- Such materials include Fe alloys, ceramics, and glass.
- the gas adsorbent 10 that adsorbs the gas in the recess is preferably stored in the recess.
- the gas adsorbent 10 that adsorbs the gas in the recess is preferably stored in the recess.
- the gas adsorbent 10 evacuates by utilizing the gas adsorption action of chemically active metal powder.
- the gas adsorbent 10 has a thickness of about 10 to 500 111 ⁇ —0: A metal plate composed mainly of Zr, Fe, V, etc. on one or both sides of a metal plate made of, etc., with a thickness of 10 m to lmm. It is made to carry.
- the surface of the metal powder of the gas adsorbing material 10 is usually covered with an acid film, so that the gas adsorbing action does not appear as it is.
- the metal powder of the gas adsorbent 10 is heated, and the surface oxide film is diffused into the adsorbent and a new active surface appears on the surface, which activates (activates) the gas adsorption action.
- the gas adsorbent 10 is attached to the lead terminal 12 by spot welding or the like, and is fixed to the fuel reformer storage container 11 in a state of being separated from the base 1 and the lid 4.
- the gas adsorbing material 10 is in a state where the force of the base 1 and the lid 4 is also lifted, and the heat of the gas adsorbing material 10 can be effectively prevented from conducting to the base 1 and the lid 4.
- a vacuum furnace It may be carried out by sealing with a brazing material or by a seam weld method in a vacuum chamber.
- the activation conditions of the gas adsorbent 10 vary depending on the type of metal powder used, but an active state can be obtained by heating the gas adsorbent 10 to about 350 to 900 ° C.
- the location where the gas adsorbent 10 is disposed is particularly the temperature formed in the fuel reformer 9 so that the gas adsorbent 10 absorbs the radiant heat from the fuel reformer 9 and is easily activated. It is desirable to arrange in the vicinity of an adjustment mechanism, for example, a heater part that also has a resistance layer isotropic force.
- the gas adsorbent 10 is formed between the fuel reformer 9 and the inner surface defining the recess of the base 1 in order to reduce heat transfer due to radiation from the fuel reformer 9 to the base 1 and the lid 4. It is desirable that the fuel reformer 9 and the lid 4 be disposed close to or in contact with the fuel reformer 9. As a result, the gas adsorbent 10 is kept activated by the heat from the fuel reformer 9 and can maintain a high gas adsorption capacity. It is possible to more effectively suppress the high-temperature surface 11 on the surface.
- the distance between the gas adsorbent 10 and the fuel reformer 9 is that the gas adsorbent 10 and the base 1
- the distance between the gas adsorbent 10 and the fuel reformer 9 is smaller than the distance between the inner surface defining the A state where the distance is smaller than the distance between them.
- the force with which the gas adsorbent 10 is in contact with the fuel reformer 9 or the distance between the gas adsorbent 10 and the fuel reformer 9 is 5 mm or less.
- the gas adsorbent 10 when the fuel reformer 9 has a substantially square shape, it is desirable that the gas adsorbent 10 be arranged so as to face the main surface of the fuel reformer 9. As a result, the main surface force of the fuel reformer 9 where more heat is released The heat conducted to the base 1 and the lid 4 can be cut off more effectively by the gas adsorbent 10, and the temperature of the gas adsorbent 10 can be increased more satisfactorily.
- the gas adsorbent 10 is disposed so as to be opposed to and parallel to the one plane.
- the gas adsorbent 10 can be opposed to many parts of the tubular fuel reformer 9, and the heat conducted to the base 1 and the lid 4 can be made more effective by the gas adsorbent 10.
- the high temperature of the gas adsorbent 10 can be improved.
- the distance between the gas adsorbent 10 and the discharge pipe 5b is set smaller than the distance between the gas adsorbent 10 and the supply pipe 5a. Good to be there.
- the reformed gas immediately after being reformed by the fuel reformer 9 is at a high temperature, and the heat of the exhaust pipe 5b that has become high temperature by the high temperature reformed gas is used to activate the gas adsorbent 10.
- the electric power for heating the gas adsorbent 10 can be further reduced, and the vacuum state inside the power loss fuel reformer storage container 11 can be kept better.
- the lead terminal 12 for fixing the gas adsorbent 10 is inserted into the base 1 and attached, but the lead terminal 12 may be inserted into the lid 4 for attachment.
- FIG. 2 is a cross-sectional view showing a fuel reformer 20A according to the second embodiment of the present invention.
- portions corresponding to the configuration of the above-described embodiment are denoted by the same reference numerals, and description thereof is omitted.
- the fuel reformer 20A includes a base, an external lead terminal 2, a lid 4, a supply pipe 5a, a discharge pipe 5b, an insulating sealing material 8, a fuel reformer 9 having an electrode 7, a gas It includes an adsorbent 10 and lead terminals 12a.
- the base body 1, the lid body 4, the supply pipe 5a and the discharge pipe 5b constitute a fuel reformer housing container 11 for housing the fuel reformer 9.
- the fuel reformer 9 and the gas adsorbing material 10 are stored in the fuel reformer storage container 11, and the recess of the base body 1 is hermetically sealed with the lid 4 to form the fuel reformer 20A.
- the lead terminal 12a is provided through a through hole formed in a side wall different from the side wall through which the external lead terminal 2 penetrates among four side walls having an inner surface defining the recess of the base body 1, The same configuration as the lead terminal 12 of the above-described embodiment.
- the gas adsorbent 10 is placed and fixed directly on the inner surface that defines the recess of the base 1, the main surface of the lid 4 on the base 1 side, and the surface of the fuel reformer 9. Or, as shown in FIG. 2, the inner surface that defines the recess of the base body 1, the main surface of the cover body 4 on the base body 1 side, or the surface of the fuel reformer 9 through a pedestal 13 that also has ceramic, metal, grease, etc. It may be mounted and fixed. Further, the gas adsorbent 10 may be fixed only to the lead terminal 12 so as to be separated from the base body 1, the lid body 4, or the fuel reformer 9.
- the gas adsorbent 10 evacuates by utilizing the gas adsorption action of chemically active metal powder.
- the gas adsorbent 10 has a thickness of about 10 to 500 111 ⁇ —0: A metal plate composed mainly of Zr, Fe, V, etc. on one or both sides of a metal plate made of, etc., with a thickness of 10 m to lmm. It is made to carry.
- the outer shape is preferably the same as that of the fuel reformer 9 so that the radiant heat from the fuel reformer 9 can be absorbed.
- the gas adsorbent 10 has a lead terminal 12a attached by spot welding or the like.
- a vacuum furnace For example, sealing with brazing material or seam welding in a vacuum chamber may be used.
- the gas adsorbent 10 is heated by being energized from the lead terminal 12a and activated.
- heating the gas adsorbent at a temperature of 350 to 900 ° C can obtain an activation state close to 100%.
- This activation means that the gas adsorbent 10 removes the oxide film formed on the surface during the manufacturing process, and a new gas adsorbing surface appears and exists in the surrounding CO, N, and H.
- the gas adsorbent 10 is disposed so as to be opposed to the high temperature portion of the fuel reformer 9 in order to absorb the radiant heat from the fuel reformer 9 and to be easily activated.
- the temperature adjusting mechanism formed in the fuel reformer 9 is disposed in the vicinity of a heater portion such as a resistance layer.
- the gas adsorbent 10 is placed on the main surface of the lid 4 on the base 1 side, but this is the inner surface defining the recess of the base 1 or the fuel reformer 9. Placed on the surface of May be. Further, it may be arranged in a gap between the fuel reformer 9 and the bottom plate of the concave portion of the base 1 or a gap between the fuel reformer 9 and the side surface of the concave portion of the base 1.
- FIG. 3 is a cross-sectional view showing a fuel reformer 20B according to a third embodiment of the present invention.
- portions corresponding to the configuration of the above-described embodiment are denoted by the same reference numerals, and description thereof is omitted.
- the fuel reformer 20B includes a base 1, an external lead terminal 2, a lid 4, a supply pipe 5a, a discharge pipe 5b, an insulating sealing material 8, and a fuel reformer 9 having an electrode 7.
- the base body 1, the lid body 4, the supply pipe 5a and the discharge pipe 5b constitute a fuel reformer storage container 11 for storing the fuel reformer 9.
- the fuel reformer 9 and the gas adsorbent 10 are stored in the fuel reformer storage container 11, and the recess of the base 1 is hermetically sealed with the lid 4 to form the fuel reformer 20B.
- the gas adsorbent 10 is provided on the surface of the fuel reformer 9.
- the gas adsorbent 10 is made of a chemically active metal powder or the like mainly composed of Zr, Fe, V, etc., and performs evacuation using the gas adsorption action. Provided on the surface.
- the fuel reformer 9 By providing the fuel reformer 9 on the surface in this way, heat transfer due to radiation from the fuel reformer 9 to the base body 1 and the lid body 4 is reduced, and the activity of the gas adsorbent 10 is reformed. It can be sustained by the heat from the vessel 9 and can maintain a higher gas adsorption capacity, and at the same time, the high-temperature suppression of the surface of the fuel reformer 11 can be more effectively suppressed.
- the electrode 7 on the fuel reformer 9 is electrically connected to the external lead terminal 2 via the bonding wire 3 or directly connected to the electrode 7 and the external lead terminal 2. Further, by sealing the concave portion of the base body 1 using the lid 4, a fuel reformer 20 B is formed in which the fuel reformer 9 accommodated in the concave portion of the base body 1 is hermetically sealed.
- the lid 4 is attached to the base body 1 so as to cover the concave portion thereof by joining or resistance welding with a metal brazing material or glass material such as Au alloy, Ag alloy, A1 alloy or the like. Accordingly, the fuel is reformed in the fuel reformer 11.
- the fuel reformer 11 is entirely heated or heated by the heat of the fuel reformer 9.
- an activation state close to 100% can be obtained by heating the gas adsorbent at a temperature of 350 to 900 ° C.
- the gas adsorbent 10 is formed on the fuel reformer 9 through a metal plate or a metal layer made of a force, preferably Ni—Cr or the like, provided on the surface of the fuel reformer 9. It is better to join it. This is because the bonding strength between the gas adsorbent 10 and the fuel reformer 9 is reinforced through the metal plate or the metal layer, and the heat released from the fuel reformer 9 is given to the metal plate or the metal layer. This is because the heat can activate the gas adsorbent 10 evenly, reduce the electric power for heating the gas adsorbent 10, and improve the power generation efficiency of the fuel cell system. Further, the gas adsorbent 10 can be activated by making the metal plate or the metal layer have a high resistance such as Ni—Cr, and by causing a current to flow through the metal plate or the metal layer to generate heat.
- a metal plate or a metal layer made of a force, preferably Ni—Cr or the like
- the metal powder having a thickness of about 10 to 500 m is supported on one side or both sides with a thickness of 10 m to lmm.
- the outer shape of the metal plate is preferably the same as that of the fuel reformer 9 so that the radiant heat from the fuel reformer 9 can be absorbed.
- the gas adsorbent 10 is attached by spot welding or the like.
- the gas adsorbent 10 is also disposed so as to be opposed to the high temperature portion of the fuel reformer 9 in order to absorb the radiant heat from the fuel reformer 9 and to be easily activated. It is good.
- the gas adsorbent 10 is disposed in the heat generating portion of the fuel reformer 9.
- the gas adsorbent 10 makes the heat conducted from the heat generating part such as the thin film heater or pressure film heater formed in the fuel reformer 9 where more heat is released to the base 1 or lid 4 more effective.
- the gas adsorbent 10 can be heated at a higher temperature.
- the gas adsorbent 10 is placed on the surface of the base 1.
- this may be placed on the inner surface of the recess of the substrate 1 or the surface of the fuel reformer 9. Further, it may be arranged in a gap between the fuel reformer 9 and the bottom plate of the recess of the base 1 or a gap between the fuel reformer 9 and the side surface of the recess of the base 1.
- FIG. 4 is a sectional view showing a fuel reformer 20C according to the fourth embodiment of the present invention.
- portions corresponding to the configuration of the above-described embodiment are denoted by the same reference numerals, and description thereof is omitted.
- the fuel reformer 20C includes a base 1, an external lead terminal 2, a lid 4, a supply pipe 5a, a discharge pipe 5b, an insulating sealing material 8, and a fuel reformer 9 having an electrode 7.
- a gas adsorbent 10 and a lead terminal 12 are included.
- the base body 1, the lid body 4, the supply pipe 5a and the discharge pipe 5b constitute a fuel reformer storage container 11 for storing the fuel reformer 9.
- the fuel reformer 9 and the gas adsorbent 10 are stored in the fuel reformer storage container 11, and the recess of the base 1 is hermetically sealed with the lid 4 to form the fuel reformer 20C.
- the fuel reformer 20C of the present embodiment is similar to the configuration of the fuel reformer 20 of the first embodiment, and it should be noted that the internal pressure of the recess is made 10 2 Pa or less.
- the fuel reformer 20C of the present embodiment is also different from the fuel reformer 20 of the first embodiment in that the lead terminal 12 is provided on the base body 1 without the insulating sealing material 8. .
- the internal pressure of the recess is set to 10 2 Pa or less.
- the internal pressure of the recess exceeds 10 2 Pa, heat is easily transferred to the base 1 and the lid 4 by the radiation of heat from the fuel reformer 9, and the self-activation of the gas adsorbent 10 occurs and gas adsorption occurs immediately.
- the activity of the material 10 tends to decrease in a short time.
- the base 1 and the lid 4 are joined by a welding method such as a projection method, a seam welder method, an electron beam method, or a laser beam method.
- a welding method such as a projection method, a seam welder method, an electron beam method, or a laser beam method.
- the bonding of the base 1 and the lid 4 by the welding method will cause the adsorption characteristics of the gas adsorbent 10 to deteriorate. To prevent this, it should be done under a low pressure of 10 2 Pa or less.
- the gas adsorbent 10 may self-activate due to the heat of reaction when adsorbing the surrounding gas, and the activation may progress, leading to deterioration of the adsorption characteristics. is there.
- the joint between the base body 1 and the lid 4 and the periphery thereof are oxidized during welding, and outgas may be released from that part as a result of the temperature during fuel reforming and over time.
- the electrode 7 on the fuel reformer 9 is electrically connected to the external lead terminal 2 provided on the substrate 1 through the bonding wire 3.
- the heater formed on the surface or inside of the fuel reformer 9 can be heated through the electrode 7.
- the reaction temperature can be maintained in the fuel reformer 9, and the fuel reforming reaction can be stabilized.
- the gas adsorbent 10 is heated by heating the metal material by transmitting electric energy from an external power source to the metal material inside the gas adsorbent through the lead terminal.
- the irradiation is performed by irradiating the gas adsorbent 10 with light rays such as infrared rays or laser light through a window provided on the substrate 1 and directly converting the energy of the light rays into heat energy with the gas adsorbent 10.
- the gas adsorbent 10 may be mounted on the fuel reformer 9 which may be mounted directly on the inner surface defining the concave portion of the substrate 1 or via a pedestal or the like. Also, as shown in Fig. 4, electrical energy from an external power source is transmitted through the lead terminal connected to the lead terminal, this electrical energy is transmitted to the metal plate of the gas adsorbent 10, and converted into thermal energy by this metal plate. Thus, the gas adsorbent 10 may be supplementarily heated.
- the gas adsorbent 10 is joined to the lead terminal 12, but it may be an insulating base such as ceramic.
- FIG. 5 is a sectional view showing a fuel reformer 20D according to the fifth embodiment of the present invention.
- FIG. 6 is a perspective view showing the upper force of the fuel reformer 20D of FIG.
- Figure 7 shows the fuel reforming of Figure 5. It is the perspective view which also looked at the lower side force of the apparatus.
- FIG. 8 is a perspective view of the base 1A of the fuel reformer 20D of FIG.
- portions corresponding to the configuration of the above-described embodiment are denoted by the same reference numerals, and description thereof is omitted.
- the fuel reformer 20D includes a base body 1A, an external lead terminal 2, a lid 4A, a supply pipe 5a, an exhaust pipe 5b, an insulating sealing material 8, and a fuel reformer 9 having an electrode 7.
- the gas adsorbent 10 and the lead terminal 12 are included.
- the base body 1A, the lid 4A, the supply pipe 5a and the discharge pipe 5b constitute a fuel reformer storage container 11 for storing the fuel reformer 9.
- the fuel reformer 9 is housed in this fuel reformer housing container and hermetically sealed with the lid 4A and the base body 1A, thereby forming the fuel reformer 2OD.
- Both the base 1A and the lid 4A in the present invention have a role as a container for storing the fuel reformer 9. They are made of, for example, stainless steel, Fe-Ni-Co alloys, Fe-based alloys such as Fe-Ni alloys, metal materials such as oxygen-free copper, inorganic materials, organic materials, or composites thereof. ing.
- the recess formed in the base 1A may be formed directly by bonding the frame to the base 1A, or the recess may be formed directly in the base 1A.
- a groove 15 for exhausting the gas in the recess is formed in at least one of the joint portion of the base body 1A of the present invention with the lid body 4A and the joint portion of the lid body 4A with the base body 1A.
- the gas inside the fuel reformer storage container 11 formed from the base 1A and the lid 4A can be sufficiently discharged from the exhaust groove 15 when sealed in a reduced pressure state.
- heat can be effectively insulated, and heat conduction from the fuel reformer 9 to the outer surfaces of the base 1A and the lid 4A can be greatly reduced. For this reason, it is possible to effectively prevent the temperature of the outer surface of the fuel reformer storage container 11 from rising.
- the force shown in the example in which the groove 15 is formed on the contact surface of the base body 1A with the lid body 4A is not limited to this, but the groove 15 is formed on the contact surface of the cover body 4A with the base body 1A. May be formed.
- the joint portion of the base 1A with the lid 4A is projected over the entire circumference, and this projecting portion (the projecting portion is generally referred to as a projection.
- the projected part is also called a projection.
- An example in which a groove 15 is formed by cutting out a part of 14 is shown.
- Such base 1A and lid 4A are formed in a predetermined shape by a cutting method, a pressing method, a MIM (Metal Injection Mold) method, or the like.
- the width of the groove 15 of the projection 14 formed on at least one of the base body 1A and the lid body 4A is preferably 0.05 mm to 5 mm.
- the surfaces thereof be subjected to a coating treatment such as a Au or Ni adhesion treatment or a resin coating such as polyimide.
- a coating treatment such as a Au or Ni adhesion treatment or a resin coating such as polyimide.
- the thickness is preferably about 0.1 to 5 / ⁇ ⁇ .
- the base body 1A and the lid body 4 ⁇ as described above should be thin in order to reduce the size and height of the fuel reformer 11, but the bending strength, which is mechanical strength, is 200. It is preferable that it is more than MPa.
- the lid 4A and the base 1A are preferably made of a metal material having a thermal conductivity of 120 W / mK or less.
- a metal material having a thermal conductivity of 120 W / mK or less As a result, heat from the fuel reformer 9 is prevented from being transmitted to the lid 4A and the base 1A, and it is possible to more effectively prevent the temperature of the lid 4A and the base 1A from rising. Become. Therefore, it is possible to more effectively prevent other parts inside the fuel reformer storage container 11 and other parts outside the fuel reformer storage container 11 from being damaged, and stabilize the fuel cell system for a long time. And can be used safely.
- Such thermal conductivity Examples of the metal material having 120 WZmK or less include stainless steel, Fe—Ni—Co alloy, Fe—Ni alloy, and the like.
- a fuel reformer 20D is formed in which the fuel reformer 9 accommodated in the chamber is hermetically sealed.
- the base body 1A and the lid body 4A are joined by welding or the like, and at the time of this welding, the inner surface defining the groove 15 is melted to close the groove 15.
- a welding method such as resistance welding or welding by laser irradiation, or a brazing method can be used.
- welding is performed while exhausting the gas inside through the groove 15, and when the welding finally reaches the vicinity of the groove 15, the inner surface defining the groove 15 is melted by the welding. Block groove 15.
- a brazing material is applied to a portion other than the groove 15, and the brazing material wets and spreads between the base body 1 A and the lid body 4 A. Close the groove 15 by spreading.
- a brazing material may be applied to the inner surface that defines the groove 15, but in this case, a sufficient passage for exhausting the gas inside the groove 15 is provided so that the groove 15 is not blocked at the time of joining. It is necessary to secure it.
- the groove 15 is finally closed by the welding method and the brazing method, so that the exhaust in the fuel reformer storage container 11 can be performed satisfactorily by the groove 15.
- the base body 1A and the lid body 4A are joined by welding, and the inner surface defining the groove 15 is melted when the base body 1A and the lid body 4A are joined to close the groove 15.
- heat can be generated only at the joint between the lid 4A and the base 1A, so that the lid 4A and the base 1A can be joined.
- the fuel reformer 9 has an external lead provided on the substrate 1A by the electrode 7 on the fuel reformer 9. 2 terminals are electrically connected. As a result, the heater formed on or inside the fuel reformer 9 can be heated through the electrode 7. As a result, the reaction temperature can be maintained in the fuel reformer 9, and the fuel reforming reaction can be stabilized.
- the gas adsorbent 10 is disposed along the inner surface on the groove 15 side that defines the recess.
- the groove 15 is used for exhaust when joining the base body 1A and the lid 4A, and the gas adsorbing material 10 is provided in a portion defining the groove 15 where gas is likely to adhere when the groove 15 is finally closed.
- the gas adhering to the portion defining the groove 15 can be immediately and efficiently adsorbed by the gas adsorbent 10.
- the efficiency of gas adsorption can be made extremely high by suppressing the vicious circle in which the gas adhering to the portion defining the groove 15 is diffused into the fuel reformer storage container and re-deposited on other parts. it can.
- the internal pressure inside the fuel reformer storage container 11, that is, the internal pressure of the recess is 10 2. Being Pa or less! /, You should be! / ...
- the base 1A and the lid 4A are joined by a resistance welding method.
- this welding method only the joint between the base 1A and the lid 4A and the vicinity thereof are heated. Therefore, it is possible to suppress the gas adsorbent 10 from being heated, and the gas adsorbent 10 is not activated when the fuel reformer storage container 11 is sealed.
- the base 1A and the lid 4A are joined under an atmospheric pressure of 10 2 Pa or less.
- the degree of vacuum in the fuel reformer storage container 11 can be increased. Therefore, it is effective that heat is transferred from the fuel reformer 9 to the base 1A and the lid 4A. Can be prevented.
- the gas adsorbent 10 When the gas adsorbent 10 is stored in the fuel reformer storage container, the gas adsorbent 10 self-activates due to the reaction heat generated when adsorbing the surrounding gas, the activation proceeds, and the adsorption characteristics It is possible to effectively prevent deterioration. In addition, when lowering the internal pressure in the fuel reformer storage container and increasing the degree of vacuum, it is possible to effectively prevent the gas adsorbent 10 from approaching the limit of the allowable amount of gas adsorption and It can be maintained well.
- the outgas discharged into the fuel reformer storage container after the fuel reformer storage container is hermetically sealed is the inner surface of the fuel reformer storage container or the surface of the fuel reformer itself. Gas adsorbed on the surface of each component in the fuel reformer storage container, or the joint between the base 1A and the lid 4A and the surrounding area during welding are oxidized, and the partial force is also the temperature during fuel reforming. It is a gas released over time and with the passage of time!
- the supply pipe 5a and the discharge pipe 5b may pass through the base body 1A or may pass through the lid body 4A. Alternatively, the inside of the recess and the outside may be communicated with each other so as to be sandwiched between the bonding interface between the base 1A and the lid 4A.
- the gas adsorbent 10 is joined to the lead terminal 12, but may be fixed to an insulating base such as ceramic.
- FIG. 9 is a cross-sectional view showing a fuel reformer 20E according to the sixth embodiment of the present invention.
- FIG. 10 is a top perspective view of the fuel reformer 20E of FIG.
- FIG. 11 is a perspective perspective view of the lower surface side of the fuel reformer 20E of FIG.
- FIG. 12 is an enlarged plan view showing a portion of the gas adsorbent 10 in the fuel reformer 20E of FIG.
- FIG. 13 is a perspective view showing the fuel reformer 20F according to the seventh embodiment of the present invention on the upper surface side excluding a part of the lid 4.
- FIG. 14 is an enlarged plan view showing a portion of the gas adsorbent 10 in the fuel reformer 20F of FIG.
- the fuel reformer 20E includes a base 1, an external lead terminal 2, a lid 4, a supply pipe 5a, a discharge pipe 5b, an insulating sealing material 8, and a fuel reformer 9 having an electrode 7. Includes a gas adsorbent 10 and a lead terminal 12b.
- the base body 1, the lid body 4, the supply pipe 5a and the discharge pipe 5b constitute a fuel reformer storage container 11 for storing the fuel reformer 9.
- the fuel reformer 9 and the gas adsorbent 10 are housed in the fuel reformer housing container 11 and the concave portion of the base body 1 is hermetically sealed with the lid 4 to form the fuel reformer 20E.
- the lead terminal 12b passes through a through hole formed in a side wall different from the side wall through which the external lead terminal 2 penetrates among the four side walls having an inner surface that defines the recess of the base body 1, and the insulating sealing material is provided on the base body 1 Except for the point provided via 8, it is configured in the same manner as the lead terminal 12 of the above-described embodiment.
- the gas adsorbent 10 is for increasing the degree of vacuum by utilizing the gas adsorption action of chemically active metal powder.
- the gas adsorbent 10 is made of, for example, 10 ⁇ m of metal powder containing Zr, Fe, V, etc. as the main component on one or both sides of a strip-like metal plate with a thickness of about 10 to 500 / ⁇ ⁇ . It is supported at a thickness of m to lmm.
- the gas adsorbent 10 is attached to the lead terminal 12b fixed to the base 1 or the lid 4 by spot welding or the like so that the inside of the recess of the base 1 communicates with the outside.
- the lead terminal 12b is for energizing the metal plate of the gas adsorbent 10.
- the lead particles 12b and the metal particles deposited on the surface of the metal plate can be heated and activated by resistance heating of the metal plate caused by energization.
- the gas adsorbent 10 can be energized by connecting a lead terminal 12b to each of both ends of the gas adsorbent 10 and applying a voltage between the lead terminals 12b connected to both ends. .
- the gas adsorbent 10 of the present invention forms a high resistance portion 16 having a smaller cross-sectional area in the direction perpendicular to the energizing direction than a portion of the energized portion of the metal plate constituting the gas adsorbent 10. is doing.
- the current-carrying portion of the metal plate refers to a portion through which a current that is input and output by the lead terminal 12b electrically connected to pass the current through the metal plate flows.
- the current input lead terminal 12b in the metal plate And the lead terminal 12b for current output.
- the gas adsorbent 10 can be efficiently activated by the high resistance portion 16, even if the gas adsorbent 10 is reduced, it is sufficient to maintain a good vacuum inside the fuel reformer storage container 11. Can maintain a good gas adsorption function. Therefore, the space for storing the gas adsorbent 10 can be reduced, and the fuel reformer storage container 11 can be reduced in size and height, and the fuel reformer storage container 11 can be used. This makes it possible to reduce the size and height of fuel cell system devices for portable devices.
- the high resistance portion 16 is formed so that the cross-sectional area in the direction orthogonal to the energization direction of the metal plate is smaller than that of other portions, and the metal plate is provided with a notch 16a that intersects the energization direction.
- the metal plate is formed by various methods such as reducing the thickness of the metal plate.
- the high resistance portion 16 is preferably formed by providing a notch 16a as shown in FIG.
- the notch 16a It is possible to suppress the occurrence of stress at the connection between the gas adsorbent 10 and the lead terminal 12b. As a result, it is possible to effectively prevent the connection portion between the lead terminal 12b and the gas adsorbent 10 from being damaged or the gas adsorbent 10 from being lost from the lead terminal 12b.
- the shape of the notch 16a provided on the metal plate of the gas adsorbent 10 can be various, such as a V shape, a square shape, or a round shape, and the notch 16a is formed in one place as shown in FIGS. 10 and 12.
- the fuel reformer 2 OF of the seventh embodiment of the present invention shown in FIGS. 13 and 14 may be formed at a plurality of locations.
- the gas adsorbent 10 is provided at equal intervals in the center or the entire length so that heat generated from the notch 16a due to energization is uniformly transmitted to the entire gas adsorbent 10.
- the gas adsorbent 10 having the notch 16a is formed by punching a metal plate made of Ni-Cr or the like carrying metal powder mainly containing Zr, Fe, V, etc. into a predetermined shape by press working. Or a method such as cutting with a laser or the like. It is formed by supporting a metal powder mainly composed of Zr, Fe, V, etc. later on a metal plate having Ni-Cr isotropic force, which is cast into a predetermined shape by the method described above.
- the gas adsorbent 10 is arranged so as to face the fuel reformer 9, and the notch 16 a is made to face the fuel reformer 9.
- the notch 16a having a particularly large heat generation of the gas adsorbent 10 is brought close to the fuel reformer 9, so that the heat of the gas adsorbent 10 is radiated to the fuel reformer 9 and the fuel reformer 9 It is possible to contribute to the high temperature of the fuel, and to reduce the power supplied to maintain the temperature of the fuel reformer 9 at a high temperature. As a result, the power generation efficiency of the fuel cell system using the fuel reformer storage container 11 can be further improved.
- the inside of the fuel reformer storage container 11 should be evacuated as much as possible! /.
- a sealing force by attaching a lid 4 to the fuel reformer storage container 11 in a vacuum furnace or There is a method of welding the lid 4 to the fuel reformer storage container 11 in the vacuum chamber by the seam weld method.
- the gas adsorbent 10 is heated by being energized from the lead terminal 12 and activated.
- an activation state close to 100% can be obtained by heating the gas adsorbent 10 at a temperature of 350 to 900 ° C.
- gas adsorbent 10 may be fixed to only the lead terminal 12b and arranged so as to be separated from the base 1, the lid 4 or the fuel reformer 9.
- the shape of the metal plate of the gas adsorbent 10 is shown as an example of a plate shape as shown in FIGS. 10 and 13, but is not limited thereto, and has a bent portion that can be a columnar shape. It may be anything. Further, the notch 16a may be formed in a groove shape on the metal plate.
- FIG. 15 is a sectional view showing a fuel reformer 20G according to the eighth embodiment of the present invention.
- portions corresponding to the configuration of the above-described embodiment are denoted by the same reference numerals, and description thereof is omitted.
- the fuel reformer 20G includes a base 1, an external lead terminal 2, a lid 4, a supply pipe 5a, a discharge pipe 5b, an insulating sealing material 8, and a fuel reformer 9 having an electrode 7. Including.
- a fuel reformer housing container 11 for housing the fuel reformer 9 is constituted by the base body 1, the lid body 4, the supply pipe 5a, and the discharge pipe 5b.
- the fuel reformer 9 is stored in the fuel reformer storage container 11 and the base body 1 is covered with the lid 4.
- the fuel reformer 20G is formed by hermetically sealing the recesses of the fuel cell.
- FIG. 16 is an enlarged cross-sectional view of the main part of the joint between the supply pipe 5a or the discharge pipe 5b and the base 1 in the fuel reformer 20G of FIG. 15 and FIG. 16, as an example of the embodiment of the supply pipe 5a or the discharge pipe 5b, an example in which a flange 6 is provided on the outside is shown.
- a gap 17 is provided between the outside of the supply pipe 5a or the discharge pipe 5b and the through hole of the base 1.
- the supply pipe 5a or the discharge pipe 5b is joined so as to have a gap 17 between the through hole formed in the base body 1 or the lid body 4.
- a gap 17 is formed when the supply pipe 5 a or the discharge pipe 5 b has the flange 6, and the flange 6 is formed in the through hole of the base body 1 or the lid 4.
- a gap 17 can be formed between the outer surface of the supply pipe 5a or the discharge pipe 5b and the inner surface of the through hole.
- FIG. 17 is an enlarged cross-sectional view of the main part of the joint between the supply pipe 5a or the discharge pipe 5b and the base 1 in the fuel reformer 20H of the ninth embodiment of the present invention. Further, as shown in FIG. 17, only a part of the outer surface of the supply pipe 5a or the discharge pipe 5b is joined to the inner surface of the through hole of the base body 1 or the lid body 4 via a brazing material or a sealing material 18.
- the gap 17 may be formed by the following.
- FIG. 18 is an enlarged cross-sectional view of a main part of a joint portion between the supply pipe 5a or the discharge pipe 5b and the base body 1 in the fuel reformer 201 according to the tenth embodiment of the present invention. Further, as shown in FIG.
- a gap 17 is formed by providing a step in the through hole of the base body 1 or the lid 4 and joining the supply pipe 5a or the discharge pipe 5b to the step by brazing or welding. May be. Further, as shown in FIG. 17, the width of the gap 17 between the outer surface of the supply pipe 5a or the discharge pipe 5b and the inner surface of the through hole of the base body 1 or the lid body 4 should be 0.01 mm or more. In addition, when only a part of the outer surface of the supply pipe 5a or the discharge pipe 5b is joined to the inner surface of the through hole of the base body 1 or the lid body 4 via the brazing material 13, it is more preferable that the thickness is 0.01 to 0.3 mm. It is good to do.
- the supply pipe 5a or the discharge pipe 5b may come into contact with the inner surface of the through-hole when the supply pipe 5a or the discharge pipe 5b is inserted into the base body 1 or the lid 4.
- the space 17 between the tube 5a or the discharge tube 5b and the through-hole may be filled with a brazing material such as Au—Sn or Ag—Cu due to capillary phenomenon, making it difficult to secure the space 17.
- a brazing material such as Au—Sn or Ag—Cu due to capillary phenomenon, making it difficult to secure the space 17.
- the heat from the fuel reformer 9 is transferred from the supply pipe 5a or the discharge pipe 5b to the base body 1, whereby the temperature of the outer wall surface of the fuel reformer storage container 11 rises and other heat in the portable device is increased. Parts destroyed It becomes easy to be done.
- the thickness is 0.3 mm or more, it is difficult to braze the supply pipe 5a or the discharge pipe 5b to the inner surface of the through hole of the base 1 or the lid 4.
- the width of the gap 17 between the inner surface and the inner surface is preferably 0.01 mm or more, more preferably 0.01 to 5 mm. If the length is less than 01 mm, the supply pipe 5a or the discharge pipe 5b may come into contact with the inner surface of the through-hole when the supply pipe 5a or the discharge pipe 5b is inserted into the base body 1 or the lid 4.
- the space 17 between the tube 5a or the discharge tube 5b and the through-hole may be filled with a brazing material such as Au—Sn or Ag—Cu by a capillary phenomenon, making it difficult to secure the space 17.
- a brazing material such as Au—Sn or Ag—Cu by a capillary phenomenon, making it difficult to secure the space 17.
- the heat from the fuel reformer 9 is transferred from the supply pipe 5a or the discharge pipe 5b to the base 1, so that the temperature of the outer wall surface of the fuel reformer storage container 11 rises. Other parts are easily destroyed.
- the heel part 6 tends to be large and deformation of the heel part 6 tends to occur.
- the fuel reformer storage container 11 itself tends to be large, which is an obstacle to downsizing and low profile.
- the outer diameter of the flange part 6 is smaller than the diameter of the through hole of the base body 1 or the lid body 4 into which the supply pipe 5a or the discharge pipe 5b is inserted. Therefore, it is preferable to increase it by 1 mm or more. Further, the thickness of the flange portion 6 is preferably 0.1 mm or more in order to prevent deformation. Further, in order to join to the base body 1 by a welding method, it is preferable to provide projections (projections) over the entire circumference of the flange portion 6 of the supply pipe 5a or the discharge pipe 5b.
- the flange 6 is directly joined to the supply pipe 5a or the discharge pipe 5b, but the cross section through which the supply pipe 5a or the discharge pipe 5b communicates has a circular shape. May be joined to the base body 1 or the lid body 4 using a polygonal cylindrical member provided with a flange 6.
- the fuel reformer storage container includes a base body having a recess in which a fuel reformer that generates reformed gas including hydrogen gas as well as a fuel is stored, and a fuel reformer power generator.
- a discharge pipe that communicates between the inside and the outside of the recess, a supply pipe that communicates the inside and outside of the recess to supply fuel to the fuel reformer, and a recess of the base are closed.
- a gas adsorbent that is accommodated in the recess and adsorbs the gas in the recess.
- the inner surface of the fuel reformer storage container and the surface of each component in the fuel reformer storage container such as the surface of the fuel reformer itself are sealed. Even if the adsorbed gas is discharged as an outgas inside the fuel reformer storage container with the influence of temperature during fuel reforming or with the passage of time, this gas is better absorbed by the gas adsorbent. Can be adsorbed. For this reason, the vacuum state inside the fuel reformer storage container can be maintained for a long period of time not only immediately after the fuel reformer is stored and sealed in the fuel reformer storage container.
- the gas adsorbing material is disposed between the fuel reformer and the inner surface of the recess or between the fuel reformer and the lid so as to be close to or in contact with the fuel reformer. Therefore, the temperature of the gas adsorbent can be increased by the heat released from the fuel reformer and the gas adsorbent can be activated, the power for heating the gas adsorbent can be reduced, and the fuel cell system Power generation efficiency can be improved.
- the gas adsorbent can absorb the heat conducted from the fuel reformer to the base and the lid, and the temperature of the outer wall surface of the fuel reformer storage container can be effectively suppressed from rising. It becomes. As a result, it is possible to effectively prevent other components in the portable device from being destroyed, and the fuel cell system can be used stably and safely over a long period of time.
- the distance between the gas adsorbent and the discharge pipe is set to be smaller than the distance between the gas adsorbent and the supply pipe.
- the heat of the exhaust pipe heated to the high temperature by the high-temperature reformed gas immediately after being reformed by the fuel reformer can be used to activate the gas adsorbent, and as a result, the gas adsorbent is heated.
- the electric power of the power generation loss fuel reformer storage container can be better maintained and the vacuum state can be kept better.
- the storage container for the fuel reformer further includes a lead terminal attached to the base so as to be led out from the inside of the recess, and the gas adsorbent is separated from the base. It is fixed to the lead terminal. Therefore, it is possible to effectively prevent the heat of the gas adsorbent from being conducted to the base and to reduce the temperature of the gas adsorbent, so that the temperature of the gas adsorbent can be maintained at a high temperature and power for heating the gas adsorbent. And the power generation efficiency of the fuel cell system can be improved.
- the gas adsorbent is formed by depositing metal powder on the surface of the metal plate, and the lead terminal for energizing the gas adsorbent is communicated between the inside of the recess and the outside. It is provided as follows. A high resistance portion having a smaller cross-sectional area in the direction orthogonal to the energizing direction than that of the other portion is formed in the energizing portion of the metal plate constituting the gas adsorbent. Accordingly, the resistance can be increased locally in the high resistance portion, and the metal powder deposited on the surface can be activated very efficiently by generating heat efficiently in the high resistance portion, and the gas adsorbent can be activated. It is possible to reduce the applied current value for dripping. As a result, the power for heating the gas adsorbent can be reduced, and the power generation efficiency of the fuel cell system using the fuel reformer storage container can be improved.
- the gas adsorbent can be efficiently activated by the high resistance section, the gas adsorbent function is sufficient to maintain a good vacuum inside the fuel reformer storage container even if the gas adsorbent is reduced. Can be maintained. As a result, the space for storing the gas adsorbent can be reduced, the fuel reformer storage container can be reduced in size and height, and the portable device using the fuel reformer storage container can be reduced. This makes it possible to reduce the size and height of fuel cell system equipment.
- the high resistance portion is formed by providing a notch in the energization portion of the metal plate. Therefore, the activation by energization from the lead terminal connected to the gas adsorbent Even when the gas adsorbent is deformed due to the effect of heat of conversion, the deformation can be mitigated by the notch, and the occurrence of stress at the connecting portion between the gas adsorbent and the lead terminal can be suppressed. As a result, it is possible to effectively prevent the connection portion between the lead terminal and the gas adsorbing material from being damaged or the gas adsorbing material from losing the lead terminal force.
- the gas adsorbent is disposed so as to face the fuel reformer, and the notch is opposed to the fuel reformer. Therefore, by bringing the notch of the gas adsorbent having a particularly large heat generation closer to the fuel reformer, the heat of the gas adsorbent can be radiated to the fuel reformer and contribute to the high temperature of the fuel reformer. In addition, the power supplied to maintain the temperature of the fuel reformer at a high temperature can be reduced. As a result, the power generation efficiency of the fuel cell system using the fuel reformer storage container can be further improved.
- the groove for exhausting the gas in the recess is formed in at least one of the joint portion of the base body to the lid body and the joint portion of the lid body to the base body. Therefore, when the lid and the base are joined in a reduced pressure state, the gas inside the fuel reformer storage container can be sufficiently discharged from the groove, and the fuel reformer storage container interior can be raised. It is possible to evacuate to vacuum. In addition, even if the base body or lid body is distorted by the heat applied when the lid body and the base body are distorted and stress is generated, the stress can be absorbed by appropriately deforming the groove, and sealing failure due to stress can occur. Can be effectively prevented.
- At least one of the joint portion of the base body with the lid body and the joint portion of the lid body with the base body is projected over the entire circumference, and a part of the projected portion is cut out.
- the groove is formed. Therefore, when heat is generated only at the joint between the lid and the base body by welding to join the lid and the base body, the heat can be concentrated on the protruding portion, and the joining efficiency can be improved. At the same time, heat is transferred to the base or lid to damage other parts in the fuel reformer storage container or other parts outside the fuel reformer storage container, or to the fuel reformer. It is possible to effectively prevent the storage container from being distorted and causing poor sealing.
- the gas adsorbent is disposed along the inner surface of the concave portion on the groove side. Therefore, the groove is used for exhaust when joining the base body and the lid, and the groove is closed when this groove is finally closed. If the gas adsorbent is brought close to the groove, the gas adhering to the groove can be immediately and efficiently adsorbed by the gas adsorbent. That is, the efficiency of gas adsorption can be made extremely high by suppressing the vicious circle in which the gas adhering to the groove is diffused into the fuel reformer storage container and reattached to other parts.
- the lid and the substrate are made of a metal material having a thermal conductivity of 120 W / mK or less. Accordingly, it is possible to further effectively prevent the temperature of the lid body surface and the substrate surface from rising by suppressing the heat generated by the fuel reformer from being transmitted to the lid body and the substrate body. This can more effectively prevent damage to other parts inside the fuel reformer storage container and other parts outside the fuel reformer storage container. It can be used stably and safely.
- the fuel cell since the fuel reformer storage container of the present invention and the fuel reformer stored in the recess are provided, the fuel cell is stable and safe for a long time and has high efficiency. A pond system can be achieved.
- the gas adsorbent is provided on the surface of the fuel reformer, even after the gas adsorbent is activated by the heat of the fuel reformer, the gas adsorbent is utilized by utilizing the heat of the fuel reformer. Can be maintained at a high temperature. Therefore, when using a gas adsorbent that has a high temperature dependence of the gas adsorption efficiency at high temperatures compared to the use at normal temperature, the gas adsorption efficiency must be very high. As a result, the vacuum state inside the fuel reformer can be maintained for a long time not only immediately after the fuel reformer is housed and sealed in the fuel reformer.
- the gas adsorbent and the fuel reformer are joined via the metal plate. Therefore, it is possible to reinforce the bonding strength between the gas adsorbent and the fuel reformer, and to apply heat to the metal plate that is also released from the fuel reformer force, and to activate the gas adsorbent evenly by the heat. In addition, the electric power for heating the gas adsorbent can be reduced, and the power generation efficiency of the fuel cell system can be improved.
- the gas adsorbent is disposed in the heat generating portion of the fuel reformer.
- the power of the heat generating part can directly heat the gas adsorbent, which can further reduce the power required to heat the gas adsorbent and improve the vacuum state inside the power generation loss fuel reformer. Can keep in good shape.
- the internal pressure of the recess is set to 10 2 Pa or less. Therefore, it is possible to effectively prevent heat from being transmitted to the base body and the lid body by the radiation of heat from the fuel reformer. In addition, by increasing the degree of vacuum around the gas adsorbent and reducing the activity of the gas adsorbent, the gas adsorbent self-activates with a little heat when the base and lid are joined. It is possible to effectively prevent the adsorption characteristic from approaching saturation.
- the lid and the substrate are joined by any one of the projection method, the seam welder method, the electron beam method, and the laser beam method. Therefore, only the joint between the base and the lid and the vicinity thereof are heated, and heat is transferred from the joint between the base and the lid through the lid to the gas adsorbent so that the gas adsorbent is activated. Can be more effectively suppressed. As a result, it is possible to more effectively prevent the gas adsorbing material from adsorbing the surrounding gas when the lid is attached and the adsorption characteristics of the gas adsorbing material to approach saturation, resulting in a decrease in the activity.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/718,189 US8182559B2 (en) | 2004-10-27 | 2005-10-27 | Fuel reformer housing container and fuel reforming apparatus |
EP05799233A EP1826175A4 (en) | 2004-10-27 | 2005-10-27 | CONTAINER FOR CONTAINING A FUEL REFORMER AND FUEL REFORMING APPARATUS |
Applications Claiming Priority (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004-312161 | 2004-10-27 | ||
JP2004-312162 | 2004-10-27 | ||
JP2004312161A JP4948759B2 (ja) | 2004-10-27 | 2004-10-27 | 燃料改質器収納用容器および燃料改質装置 |
JP2004312162A JP2006124208A (ja) | 2004-10-27 | 2004-10-27 | 燃料改質器収納用容器および燃料改質装置 |
JP2004371319A JP5046484B2 (ja) | 2004-12-22 | 2004-12-22 | 燃料改質器収納用容器および燃料改質装置 |
JP2004-371319 | 2004-12-22 | ||
JP2004-375035 | 2004-12-24 | ||
JP2004375036A JP4889217B2 (ja) | 2004-12-24 | 2004-12-24 | 燃料改質装置の製造方法 |
JP2004-375036 | 2004-12-24 | ||
JP2004375035A JP2006182573A (ja) | 2004-12-24 | 2004-12-24 | 燃料改質装置 |
JP2005-017865 | 2005-01-26 | ||
JP2005017865A JP2006206352A (ja) | 2005-01-26 | 2005-01-26 | 燃料改質器収納用容器および燃料改質装置 |
JP2005021183A JP2006206388A (ja) | 2005-01-28 | 2005-01-28 | 燃料改質器収納用容器および燃料改質装置ならびに燃料改質装置の製造方法 |
JP2005-021183 | 2005-01-28 |
Publications (1)
Publication Number | Publication Date |
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WO2006046646A1 true WO2006046646A1 (ja) | 2006-05-04 |
Family
ID=36227888
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/019790 WO2006046646A1 (ja) | 2004-10-27 | 2005-10-27 | 燃料改質器収納用容器および燃料改質装置 |
Country Status (3)
Country | Link |
---|---|
US (1) | US8182559B2 (ja) |
EP (1) | EP1826175A4 (ja) |
WO (1) | WO2006046646A1 (ja) |
Cited By (6)
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JP2006143542A (ja) * | 2004-11-22 | 2006-06-08 | Kyocera Corp | 燃料改質器収納用容器および燃料改質装置 |
JP2006155953A (ja) * | 2004-11-25 | 2006-06-15 | Kyocera Corp | 燃料改質器収納用容器および燃料改質装置ならびに燃料改質システム |
JP2006176379A (ja) * | 2004-12-24 | 2006-07-06 | Kyocera Corp | 燃料改質器収納用容器および燃料改質装置 |
EP2062851A1 (en) * | 2006-08-30 | 2009-05-27 | Kyocera Corporation | Reaction device, fuel battery system, and electronic device |
EP2072461A1 (en) * | 2006-08-30 | 2009-06-24 | Kyocera Corporation | Reaction device, fuel battery system, and electronic device |
EP2072460A1 (en) * | 2006-08-30 | 2009-06-24 | Kyocera Corporation | Reaction device, fuel cell system, and electronic apparatus |
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CN102884618B (zh) * | 2010-09-28 | 2015-07-22 | 京瓷株式会社 | 元件收纳用容器及使用其的电子装置 |
CN102956662B (zh) * | 2012-11-22 | 2015-01-28 | 烟台睿创微纳技术有限公司 | 一种红外焦平面探测器芯片真空密封封装结构及封装方法 |
EP3051582B1 (en) * | 2013-09-27 | 2020-01-22 | Kyocera Corporation | Lid body, package, and electronic apparatus |
WO2020044321A1 (en) * | 2018-08-31 | 2020-03-05 | Ecole Polytechnique Federale De Lausanne (Epfl) | Fuel cell system for portable applications |
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- 2005-10-27 US US11/718,189 patent/US8182559B2/en not_active Expired - Fee Related
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JP2006143542A (ja) * | 2004-11-22 | 2006-06-08 | Kyocera Corp | 燃料改質器収納用容器および燃料改質装置 |
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EP2072461A1 (en) * | 2006-08-30 | 2009-06-24 | Kyocera Corporation | Reaction device, fuel battery system, and electronic device |
EP2072460A1 (en) * | 2006-08-30 | 2009-06-24 | Kyocera Corporation | Reaction device, fuel cell system, and electronic apparatus |
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EP2072461A4 (en) * | 2006-08-30 | 2011-11-02 | Kyocera Corp | Reaction device, fuel cell system and electronic device |
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Also Published As
Publication number | Publication date |
---|---|
EP1826175A4 (en) | 2010-12-01 |
US20090229181A1 (en) | 2009-09-17 |
EP1826175A1 (en) | 2007-08-29 |
US8182559B2 (en) | 2012-05-22 |
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