[go: up one dir, main page]

WO2005115912A1 - Appareil de production d’hydrogène et système à cellule électrochimique utilisant l’appareil - Google Patents

Appareil de production d’hydrogène et système à cellule électrochimique utilisant l’appareil Download PDF

Info

Publication number
WO2005115912A1
WO2005115912A1 PCT/JP2005/009553 JP2005009553W WO2005115912A1 WO 2005115912 A1 WO2005115912 A1 WO 2005115912A1 JP 2005009553 W JP2005009553 W JP 2005009553W WO 2005115912 A1 WO2005115912 A1 WO 2005115912A1
Authority
WO
WIPO (PCT)
Prior art keywords
reforming catalyst
reforming
catalyst
catalyst bed
hydrogen generator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/009553
Other languages
English (en)
Japanese (ja)
Inventor
Yukimune Kani
Kunihiro Ukai
Hidenobu Wakita
Kiyoshi Taguchi
Seiji Fujihara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of WO2005115912A1 publication Critical patent/WO2005115912A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
    • B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00477—Controlling the temperature by thermal insulation means
    • B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • 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 hydrogen generator for reforming a hydrocarbon-based raw material to generate hydrogen for supply to a fuel cell, and a fuel cell system using the same.
  • a fuel cell system capable of high-efficiency small-scale power generation can easily construct a system for utilizing thermal energy generated at the time of power generation, and can achieve high energy use efficiency. It is suitably used as a distributed power generation system.
  • the fuel cell system has a fuel cell as a main body of the power generation unit.
  • a fuel cell such as a polymer electrolyte fuel cell (hereinafter referred to as PEFC) or a phosphoric acid fuel cell (hereinafter referred to as PAFC) is generally used.
  • PEFC polymer electrolyte fuel cell
  • PAFC phosphoric acid fuel cell
  • these fuel cells such as PEFC and PAFC require hydrogen gas (hereinafter simply referred to as hydrogen) as a fuel for power generation. Therefore, usually, a fuel cell system is provided with a hydrogen generator for generating hydrogen required for power generation.
  • a fuel raw material is reformed to generate hydrogen by a predetermined hydrogen generation method.
  • the predetermined hydrogen generation method include water electrolysis, a steam reforming method in which hydrocarbon-based raw materials are reformed to generate hydrogen, a partial oxidation method, and an autothermal method in which both are combined.
  • raw materials for fuels such as methane, ethane, propane, butane, city gas, LP gas, and other hydrocarbon-based gases (including a mixture of two or more hydrocarbon-based gases) are used.
  • Hydrogen is generated by reforming by a predetermined reforming reaction.
  • the steam reforming method hydrogen is generated by reforming any of the raw materials using steam.
  • power generation is performed using reformed gas (hydrogen contained in reformed gas) rich in hydrogen discharged from the hydrogen generator and air (oxygen in the air).
  • the raw material introduced into the reformer of the hydrogen generator contains abundant hydrogen by a steam reforming reaction between the raw material and steam inside the reformer. Is converted to high quality gas.
  • This steam reforming reaction proceeds by using a reforming catalyst having a catalytic metal such as a nickel-based catalyst (hereinafter, nickel is referred to as “Ni”) or a ruthenium-based catalyst (hereinafter, ruthenium is referred to as “Ru”).
  • the steam reforming reaction proceeds by being heated to a temperature of about 400 ° C. to 700 ° C. in the reforming catalytic power S.
  • the reformed gas discharged from the reformer includes unreacted raw materials (such as methane), unreacted steam and carbon dioxide, and carbon monoxide (hereinafter referred to as CO). Is contained as a by-product. These by-products are usually contained at about 8 to 15% by volume, depending on the performance of the reformer and the operating temperature of the hydrogen generator.
  • the limit of the CO content in the reformed gas supplied to the PEFC is about 50 ppm, and if it exceeds this limit, the power generation performance of the fuel cell will be significantly degraded. Therefore, in fuel cell systems, it is necessary to reduce the CO content of the reformed gas as much as possible before supplying it to the PEFC.
  • the reformed gas discharged from the reformer is introduced into a converter provided after the begging reformer for reducing the unnecessary CO content.
  • CO in the reformed gas into which the reformer power is also introduced is converted into carbon dioxide gas by a shift reaction with water shown in chemical formula (1).
  • hydrogen is generated together with the generation of carbon dioxide gas. Due to the shift reaction between CO and water in this converter, the CO concentration in the reformed gas is reduced to about 0.5% by volume.
  • the reformed gas that has also discharged the reformer power is sent to a purifier that is provided after the converter that further reduces the CO content to a level that can be supplied to PEFC. Further introduced.
  • CO in the reformed gas introduced into the converter is converted to carbon dioxide by an oxidation reaction between CO shown in chemical formula (2) and an oxidizing gas such as oxygen. Is replaced.
  • the CO concentration in the reformed gas is reduced to 50 ppm or less, preferably 1 Oppm or less.
  • high-quality reformed gas rich in hydrogen with sufficiently reduced CO content is discharged from the hydrogen generator by the steam reforming reaction, shift reaction, and oxidation reaction. Then, the high-quality reformed gas power rich in hydrogen purified in this way is supplied to the fuel electrode side of a fuel cell such as PEFC or PAFC.
  • the fuel raw material supplied to the hydrogen generator in order to generate hydrogen often contains a sulfur sulfide.
  • city gas and LP gas are added from the viewpoint of safety of odorants such as sulfides and mercaptanes in order to facilitate detection of leaks.
  • the effect of sulfur on the reforming reaction varies depending on the type of catalyst used.In particular, in the case of a reforming catalyst used in a steam reforming reaction, even when sulfur is present at a low concentration, its catalytic activity is low. Decreases. For this reason, raw materials such as city gas and LP gas supplied to the hydrogen generator are desulfurized and then introduced into the reformer of the hydrogen generator.
  • the low-temperature part of the reforming catalyst is filled with the high heat-resistant reforming catalyst premised on use at a high temperature as described above, so that sufficient low-temperature activity cannot be obtained in the low-temperature part.
  • the reformer there is a problem that sufficient catalytic activity cannot be obtained in the low temperature part. This leads to poor conversion of the raw material.
  • Patent Document 1 Japanese Patent No. 3242514
  • Patent Document 2 Japanese Patent No. 1964213
  • Patent Document 3 JP-A-8-217403
  • the raw material such as city gas or LP gas for producing hydrogen is used. It is said that the composition of the desulfurization unit is complicated because hydrogen is added and the sulfur compound is decomposed into hydrocarbons and hydrogen sulfide by hydrotreatment under high temperature and high pressure conditions to reduce the sulfur concentration. There's a problem.
  • the conventional reformer slightly large particles of the catalyst metal are usually supported by a carrier so that the sintering of the catalyst metal does not significantly change during the steam reforming reaction, and the physical properties thereof do not significantly change. Equipped with a reforming catalyst. Therefore, the conventional reformer basically has a problem that sulfur adsorption capacity is small with respect to sulfur poisoning. Therefore, the conventional reformer basically has a problem that metals, which are valuable resources such as Ni and Ru, are effectively used.
  • a reforming catalyst is constituted by using a large amount of catalyst metal, the adsorption capacity of sulfur is greatly increased. Therefore, the sulfur-containing compound contained in the raw material without using a desulfurization device having a complicated structure is required. Objects can be effectively removed.
  • this configuration in a configuration using a reforming catalyst that emphasizes thermal stability, even when the temperature near the inlet of the reforming catalyst is reduced and sufficient catalytic activity cannot be obtained in the low temperature portion, In addition, deterioration of the conversion rate of the raw material can be suppressed.
  • the size of the reformer is increased due to the increase in the size of the reforming catalyst, so that the fuel cell system is increased in size.
  • the present invention has been made in order to solve the above-mentioned problems, and has been proposed in order to improve the conversion rate of a fuel material to hydrogen and to exhibit a long-life hydrogen having a stable operation with a large sulfur adsorption capacity.
  • An object of the present invention is to provide a generator and a fuel cell system using the same. Means for solving the problem
  • a hydrogen generator provides a reformer that generates a reformed gas containing hydrogen by a reforming reaction using at least a mixed gas of a hydrocarbon-based raw material and water. And to the reformer! Hydrogen generation, comprising: a reforming catalyst bed through which the mixed gas flows and progresses the reforming reaction of the mixed gas; and a heater for heating the reforming catalyst bed for the reforming reaction.
  • the apparatus wherein the number of catalytically active points per unit volume at an inflow portion of the mixed gas of the reforming catalyst bed is larger than the number of catalytically active points per unit volume at an outflow portion of the mixed gas of the reforming catalyst bed.
  • the number of catalytically active points per unit volume at the mixed gas inflow section of the reforming catalyst bed can be reduced by the number of catalytically active points per unit volume at the mixed gas outflow section of the reforming catalyst bed. Therefore, the reforming catalyst on the downstream side of the gas flow is less susceptible to the deterioration due to the poisoning of the sulfur-containing compound, so that stable operation of the hydrogen generator can be guaranteed. Become.
  • the number of catalytic active points in the reforming catalyst bed may decrease stepwise from the inflow section to the outflow section. Further, in this case, the number of catalytically active points in the reforming catalyst bed may decrease continuously from the inflow section to the outflow section.
  • the number of catalytic active points in the reforming catalyst bed decreases stepwise or continuously toward the inflow section and the outflow section, so that the influence of deterioration due to poisoning of the sulfur compound is obtained. It is possible to obtain a suitable hydrogen generator that is less likely to be affected and operates stably.
  • the average particle diameter of the catalyst metal at the inflow section of the reforming catalyst bed is smaller than the average particle diameter of the catalyst metal at the outflow section of the reforming catalyst bed.
  • the surface area per unit volume at the inflow portion of the reforming catalyst bed is larger than the surface area per unit volume at the outflow portion of the reforming catalyst bed.
  • the number of catalytic active points per unit volume on the upstream side of the gas flow in the reforming catalyst bed can be suitably increased.
  • the catalyst metal content per unit volume at the inflow portion of the reforming catalyst bed is larger than the catalyst metal content per unit volume at the outflow portion of the reforming catalyst bed.
  • the temperature at the time of the reforming reaction at the inflow portion of the reforming catalyst bed is lower than the temperature at the time of the reforming reaction at the outflow portion of the reforming catalyst bed.
  • the temperature at the time of the reforming reaction in the inflow section of the reforming catalyst bed is 50
  • the temperature during the reforming reaction at the outlet of the reforming catalyst bed is 700 ° C or less.
  • a fuel cell system includes the hydrogen generator according to claim 1 and a fuel cell that is a main body of a power generation unit, and at least the reformed gas discharged from the hydrogen generator is discharged by the fuel cell. The power is supplied to the fuel cell to generate power and output power.
  • the present invention is implemented by the means described above to improve the conversion rate of a fuel raw material to hydrogen and to produce long-life hydrogen that exhibits stable operation with a large sulfur adsorption capacity.
  • Device and a fuel cell system using the same. can get.
  • FIG. 1 is a block diagram schematically showing a configuration of a fuel cell system according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an internal configuration of a reformer according to an embodiment of the present invention.
  • FIG. 3 is a block diagram schematically showing a configuration of an atmospheric pressure flow type reaction apparatus according to Example 1 of the present invention.
  • FIG. 4 is a correlation diagram showing the results of evaluating the effect of the reaction temperature on the catalytic activity of the reforming catalyst according to Example 1 of the present invention.
  • FIG. 5 is a correlation diagram showing the result of evaluating the effect of the reaction temperature on the catalytic activity (methane conversion ratio) of the reforming catalyst according to Example 1 of the present invention.
  • FIG. 6 is a correlation diagram showing evaluation results regarding sulfur poisoning of the reforming catalyst according to Example 2 of the present invention.
  • FIG. 7 is a block diagram schematically showing a configuration of a second normal-pressure flow reactor according to Embodiment 3 of the present invention.
  • FIG. 8 is a correlation diagram showing the results of evaluating the effect of the reaction temperature on the catalytic activity (methane conversion ratio) of the reforming catalyst according to Example 3 of the present invention.
  • FIG. 9 is a correlation diagram showing the results of evaluating the effect of the average particle size of the catalytic metal on the catalytic activity (methane conversion) of the reforming catalyst according to Example 4 of the present invention.
  • FIG. 10 is a correlation diagram showing the number of catalytically active points per unit volume of Ru-based catalyst E and Ru-based catalyst F according to Example 5 of the present invention and the surface area after supporting Ru.
  • FIG. 11 is a correlation diagram showing the results of evaluating the effect of the surface area of the catalyst body on the catalytic activity (methane conversion) of the reforming catalyst according to Example 5 of the present invention.
  • FIG. 12 is a correlation diagram showing the weight percent of Ru and the number of catalytically active points per unit volume of Ru-based catalyst G and Ru-based catalyst H according to Example 6 of the present invention.
  • FIG. 13 is a graph showing that the Ru amount according to Example 6 of the present invention shows the catalytic activity (reaction of methane
  • FIG. 7 is a correlation diagram showing the results of evaluating the effect on ().
  • FIG. 14 is a correlation diagram showing the results of evaluating the catalytic activity of a reforming catalyst when a honeycomb catalyst according to Example 7 of the present invention was used.
  • FIG. 15 is a correlation diagram showing the results of evaluating the catalytic activity of the reforming catalyst when the reforming catalyst according to Example 8 of the present invention was diluted and used.
  • FIG. 16 is a block diagram schematically showing a configuration of a third normal-pressure flow reactor according to Embodiment 9 of the present invention.
  • FIG. 17 is a correlation diagram showing the results of evaluating the catalytic activity of the reforming catalyst when the number of stages of the reforming catalyst according to Example 9 of the present invention was increased.
  • FIG. 1 is a block diagram schematically showing a configuration of a fuel cell system according to an embodiment of the present invention.
  • a fuel cell system 100 of the present embodiment has a hydrogen generator 101 and a fuel cell 9 as main components.
  • the hydrogen generator 101 discharges a reformed gas rich in hydrogen by using a desulfurized fuel raw material and vaporized reforming water.
  • the reformed gas discharged from the hydrogen generator 101 is supplied to the fuel electrode side of the fuel cell 9. Then, in the fuel cell 9, power generation is performed to output electric power by using the reformed gas and air supplied to the fuel electrode side.
  • the fuel cell system 100 includes a material supply device 1 and a material desulfurization device 2.
  • Raw materials supplied to the raw material desulfurization unit 2 by the raw material supply unit 1 include natural gas, methanol, gasoline, and the like. However, in the present embodiment, natural gas is used as a raw material.
  • the raw material supply device 1 has a booster capable of constantly supplying natural gas and boosting the natural gas from the infrastructure not shown in FIG. 1.
  • the raw material desulfurization device 2 has a zeolite-based adsorbent for adsorbing sulfur compounds.
  • the infrastructure and the raw material supply device 1 are connected by a pipe a.
  • the natural gas supplied from the infrastructure car is supplied to the raw material supply device 1 through the pipe a.
  • the raw material supply device 1 and the raw material desulfurization device 2 are connected by a pipe b.
  • natural gas is supplied from the raw material supply device 1 to the raw material desulfurization device 2 through the pipe b.
  • the raw material desulfurization device 2 and the hydrogen generation device 101 are connected by a pipe c.
  • the raw material desulfurized by the raw material desulfurization device 2 is supplied to the hydrogen generator 101 through this pipe c.
  • the fuel cell system 100 includes a reformed water supply device 3 and an evaporator 4.
  • the reforming water supply device 3 has a plunger pump capable of supplying reforming water from a water tank 15 described later to the evaporator 4.
  • the evaporator 4 has a heater for evaporating water. Although the details of the evaporator 4 are not shown, the heat of the reformer power is supplied to the heater to be heated.
  • the water tank 15 and the reformed water supply device 3 are connected by a pipe n.
  • the water for reforming or cooling stored in the water tank 15 is supplied to the reformed water supply device 3 through the pipe n. Further, the reforming water supply device 3 and the evaporator 4 are connected by a pipe o. Through this pipe o, reforming water is supplied from the reforming water supply device 3 to the evaporation device 4. Further, the evaporator 4 is connected to a predetermined position of the pipe c by a pipe p. The reforming water vaporized by the evaporator 4 is mixed with the desulfurized raw material flowing through the pipe c through the pipe p. Then, the mixture of the mixed raw material and water is supplied to the hydrogen generator 101 through the pipe c.
  • the hydrogen generator 101 heats the reformer 5 where reformed gas is generated by the steam reforming reaction and the reformer 5 to a temperature required for the steam reforming reaction. And the shift reaction to reduce the CO content in the reformed gas.
  • a predetermined space in the reformer 5 is filled with a reforming catalyst for catalyzing a steam reforming reaction.
  • a reforming catalyst in which Ru is supported on alumina as a heat-resistant carrier is used as the reforming catalyst.
  • a predetermined space in the shift converter 6 is filled with a shift catalyst for catalyzing a shift reaction.
  • the shift catalyst a shift catalyst in which platinum (hereinafter referred to as Pt) is supported on a ceria-zirconia-based carrier is used here.
  • a predetermined space in the purifier 7 is filled with an oxidation catalyst for catalyzing an oxidation reaction for oxidizing CO.
  • the oxidation catalyst used here is a CO oxidation catalyst supporting Ru on alumina.
  • the reforming heater 17 mainly includes a small dehumidified reformed gas (this is referred to as off-gas) used for power generation discharged from the condenser 13 described later. It has a burner that is used for combustion. The reformer 5 is heated and kept at a predetermined temperature required for the steam reforming reaction by burning off-gas in the burner of the reforming heater 17.
  • off-gas small dehumidified reformed gas
  • the air supply device 8 is constituted by a blower capable of continuously supplying air.
  • the reformed gas generated in the reformer 5 is supplied to the shift converter 6 through the pipe d.
  • the transformer 6 and the purifier 7 are connected by a pipe e.
  • the reformed gas whose CO content has been reduced in the shift converter 6 is supplied to the purifier 7 through this pipe e.
  • the air supply device 8 and a predetermined position of the pipe e are connected by a pipe g.
  • a pipe f is connected to an air intake of the air supply device 8.
  • the air supply device 8 sends the air introduced through the pipe f to the pipe g by the blower, thereby supplying air into the pipe e. That is, the mixed gas of the reformed gas and the air from the converter 6 mixed in the pipe e is supplied to the purifier 7.
  • the reforming heater 17 and the condenser 13 are connected by a pipe u.
  • the dehumidified reformed gas used for power generation is supplied from the condenser 13 to the reforming heater 17.
  • a pipe h extends from the purifier 7, and through this pipe h, reformed gas rich in hydrogen generated and purified by the hydrogen generator 101 is supplied to the fuel cell 9.
  • the catalyst filled in the reformer 5, the shift converter 6, and the purifier 7 is a catalyst generally used in a hydrogen generator, and the present invention can be applied to other catalysts having the same function. The effect of this does not change.
  • a Ni catalyst is used as the reforming catalyst
  • a Cu—Zn catalyst or Fe—Cr catalyst is used as the shift catalyst
  • a Pt catalyst or the like is used as the oxidation catalyst.
  • the fuel cell 9 the reformed gas (hydrogen in the reformed gas) supplied from the hydrogen generator 101 via the pipe h, and the air supply unit 16 to be described later via the pipes j, k and 1
  • the supplied air oxygen in the air
  • the fuel cell 9 is configured to use a solid polymer electrolyte membrane. That is, the fuel cell 9 shown in the present embodiment is a PEFC.
  • the fuel cell 9 generates heat during power generation, but is appropriately cooled by cooling water supplied from a water tank 15 described later. As a result, the fuel cell 9 exhibits a predetermined power generation performance.
  • the fuel cell system 100 includes a cooling water circulating device 10 that supplies cooling water for cooling the fuel cell 9, and a cooling water temperature detector that detects the temperature of the cooling water flowing inside the fuel cell 9. 12, a heat exchanger 11 for radiating the heat of the raised cooling water used for cooling the fuel cell 9 to the outside and humidifying the air supplied to the fuel cell 9, and a heat exchanger 9 for the fuel cell 9.
  • An air supply device 16 for supplying air required for power generation.
  • the cooling water circulation device 10 has, for example, a plunger pump capable of supplying cooling water to the fuel cell 9 from a water tank 15 described later.
  • the cooling water temperature detector 12 is constituted by, for example, a thermistor.
  • the heat exchange 11 has a perfluorosulfonic acid resin film here.
  • the air supply device 16 is configured using a blower or the like capable of continuously supplying air.
  • the hydrogen generator 101 and the fuel cell 9 are connected by the pipe h. Has been.
  • the reformed gas discharged from the hydrogen generator 101 is supplied to the fuel electrode side of the fuel cell 9 through the pipe h.
  • the cooling water circulation device 10 and a cooling water passage (not shown) of the fuel cell 9 are connected by a pipe r.
  • the cooling water circulation device 10 and a water tank 15 described later are connected by a pipe q. That is, the cooling water supplied from the water tank 15 is supplied to the fuel cell 9 via the pipe q, the cooling water circulation device 10, and the pipe r.
  • a drain port of the cooling water channel of the fuel cell 9 and the heat exchange II are connected by a pipe s.
  • Cooling water whose temperature has risen and is discharged from the fuel cell 9 is supplied to the heat exchanger 2 through the pipe s.
  • the heat exchanger II and the water tank 15 are connected by a pipe t, and the cooling water cooled by the heat exchanger II is returned to the water tank 15 through the pipe t.
  • the air electrode side of the fuel cell 9 and the heat exchange 11 are connected by a pipe 1, and the heat exchange 11 and the air supply device 16 are connected by a pipe k.
  • the air supplied by the air supply device 16 passes through the pipe k, is humidified to a predetermined humidity by the heat exchanger 11, and is then supplied to the fuel cell 9 through the pipe 1.
  • the air supply device 16 is connected to a pipe j for introducing air.
  • the air supply device 16 supplies the air introduced from the pipe j to the fuel cell 9 via the heat exchange 11.
  • the fuel cell system 100 includes a condenser 13 for dehumidifying reformed gas (off gas) and air not used for power generation discharged from the fuel cell 9 and condensing air, and water discharged from the condenser 13. It has a water purification device 14 for purifying water and a water tank 15 for storing water purified by the water purifying device 14.
  • the condenser 13 condenses the water contained in the off-gas and the air by a predetermined condensing mechanism, whereby the dried off-gas is sent to the reforming heater 17, while the dried air is sent to the atmosphere. Into each release.
  • the purification apparatus 14 is configured using an ion exchange resin containing a styrene-based thione exchange resin having a sulfonic acid group and a weakly basic ion exchange resin.
  • the condenser 13 and the fuel cell 9 are connected by a pipe m and a pipe i. Energized air not used for power generation, which is discharged from the fuel cell 9, is supplied to the condenser 13 through the pipe m. Further, the fine reformed gas discharged from the fuel cell 9 and not used for power generation is supplied to the condenser 13 through the pipe i. Further, as described above, the condenser 13 and the reforming heater 17 are connected by the pipe u.
  • Condenser 13 The dehumidified off-gas from which power is also discharged is supplied to the reforming heater 17 through this pipe u.
  • the condenser 13 and the water purifier 14 are connected by a pipe V, and the water purifier 14 and the water tank 15 are connected by a pipe w.
  • the water discharged by the condensation from the condenser 13 is returned to the water tank 15 through the pipe V and the pipe w.
  • the fuel cell system 100 has a control device for appropriately controlling the operation of each of the components.
  • the fuel cell system 100 performs a predetermined power generation operation by appropriately controlling the operation of the fuel cell system 100.
  • FIG. 2 is a cross-sectional view schematically showing an internal configuration of the reformer according to the embodiment of the present invention.
  • reformer 5 of hydrogen generator 101 has basically the same configuration as that of a general reformer. That is, the reformer 5 is provided with a supply port 20a to which a mixed gas of the desulfurized raw material supplied from the pipe c shown in FIG. 1 and steam is supplied, and a steam reforming reaction communicating with the supply port 20a. A first space 23a where the mixed gas is used, a reforming catalyst 103 that catalyzes a steam reforming reaction using the mixed gas, and a second space 23b where a reformed gas generated by the steam reforming reaction is introduced.
  • a reforming heater 17 for supplying heat required for the steam reforming reaction to the reforming catalyst 103 to an outlet 20b through which the reformed gas introduced into the second space 23b is discharged.
  • a reforming heater 17 is provided at the center of the reformer 5.
  • a first space 23a through which the mixed gas introduced from the supply port 20a flows and moves is formed.
  • the reforming catalyst 103 is provided inside the first space 23a by a predetermined fixing means. Outside the first space 23a, there is formed a second space 23b into which the reformed gas generated by the steam reforming reaction flows and moves.
  • the second space 23b communicates with the first space 23a below the reformer 5. Further, the second space 23b communicates with the outlet 20b. That is, in the reformer 5, the supply port 20a, the first space 23a, the second space 23b, and the discharge port 20b communicate with each other, and the supply port 20a, the first space 23a, and the second space 23a communicate with each other.
  • the reforming catalyst 103 is provided in the middle of the flow path formed by the space 23b and the discharge outlet 20b.
  • the reforming catalyst 103 is composed of two first reforming catalysts Ru and a second reforming catalyst 22. It is composed of different reforming catalysts.
  • the first Ru-based reforming catalyst 21 has a lower temperature, and the mixed gas inflow side (gas gas) in the reforming catalyst 103 which is hardly affected by sintering. (On the upstream side of the flow).
  • the second Ru-based reforming catalyst 22 is disposed on the outflow side (downstream of the gas flow) of the mixed gas in the reforming catalyst 103. That is, the reforming catalyst 103 is composed of two different reforming catalysts, the Ru-based reforming catalyst 21 on the upstream side of the gas flow and the Ru-based reforming catalyst 22 on the downstream side of the gas flow.
  • the Ru-based reforming catalyst 21 on the gas flow upstream side is compared with the Ru-based reforming catalyst 22 on the gas flow downstream side
  • the Ru-based reforming catalyst on the gas flow upstream side is compared.
  • 21 has a larger number of catalytically active sites per unit volume than the Ru-based reforming catalyst 22 on the downstream side of the gas flow.
  • the Ru-based reforming catalyst 21 has a smaller average particle diameter of the catalyst metal constituting the reforming catalyst than the Ru-based reforming catalyst 22. .
  • the Ru-based reforming catalyst 21 has a larger surface area per unit volume (BET surface area) than the Ru-based reforming catalyst 22. Further, in the Ru-based reforming catalyst 21 and the Ru-based reforming catalyst 22, the Ru-based reforming catalyst 21 has a higher content of catalytic metal per unit volume than the Ru-based reforming catalyst 22.
  • the number of catalytically active points per unit volume of Ru-based reforming catalyst 21 is 18 ⁇ molZcc, and the number of catalytically active points per unit volume of Ru-based reforming catalyst 22 is 4 ⁇ molZcc.
  • the average particle diameter of the catalyst metal in the Ru-based reforming catalyst 21 is 15 nm, and the average particle diameter of the catalyst metal in the Ru-based reforming catalyst 22 is 23 nm.
  • the surface area per unit volume of the Ru-based reforming catalyst 21 is 98 m 2 / g, and the surface area per unit volume of the Ru-based reforming catalyst 22 is 4 m 2 / g.
  • the catalyst metal content per unit volume of the Ru-based reforming catalyst 21 is 0.03 g / cc
  • the catalyst metal content per unit volume of the Ru-based reforming catalyst 22 is [0069]
  • the steam reforming reaction in the reformer 5 is performed at a temperature suitable for the reforming reaction when each of the Ru-based reforming catalyst 21 upstream of the gas flow and the Ru-based reforming catalyst 22 downstream of the gas flow. Heating is controlled by the reforming heater 17 so that the process proceeds effectively.
  • the reforming heater 17 heats the reforming catalyst 103 by heat generated by burning off-gas discharged from the fuel cell 9 and dehumidified by the condenser 13.
  • the raw materials supplied to the reformer 5 include natural gas, methanol, gasoline and the like.
  • Examples of the method for reforming the raw material include a steam reforming method in which steam is reformed and a partial reforming method in which air is added to reform.
  • the present invention is not limited to natural gas and a steam reforming method, here, a case where a natural gas is obtained as a raw material and a reformed gas is obtained using a steam reforming method as a reforming method is described. I will tell you.
  • the fuel cell system 100 it is necessary to remove the sulfur-containing compound contained in the raw material before supplying the raw material to the hydrogen generator 101. Introduced from equipment 1 to raw material desulfurization equipment 2. By the desulfurization action of the raw material desulfurization device 2, the sulfur component contained in the raw material is selectively adsorbed by the adsorbent. That is, the concentration of the sulfur compound contained in the raw material is reduced by the raw material desulfurization device 2 to about 1 to about LOppb. The raw material in which the concentration of the sulfur conjugate has been reduced is then mixed with steam and supplied to the reformer 5 of the hydrogen generator 101.
  • the water is supplied from the hydraulic water tank 15 necessary for the steam reforming reaction in the reformer 5 to the evaporator 4 through the reforming water supply device 3.
  • the water supplied from the reformed water supply device 3 is heated to be steam.
  • the steam generated in the evaporator 4 is mixed with the desulfurized raw material discharged from the raw material desulfurizer 2. Then, as described above, the mixed gas of the desulfurized raw material and the steam is supplied to the reformer 5 of the hydrogen generator 101.
  • the reformer 5 When a mixed gas of natural gas and steam is supplied to the reformer 5 of the hydrogen generator 101, the reformer 5 has a high-temperature reforming catalyst (the reforming catalyst shown in FIG. 2). Quality catalyst 103) The reformed gas rich in hydrogen is generated by the steam reforming reaction catalyzed by hydrogen. The reformed gas generated in the reformer 5 contains unreacted raw materials (natural gas in this case), steam, CO, and the like as about 8 to 15% by volume as by-products.
  • the catalytic activity of the reforming catalyst decreases with time. This is because the reforming catalyst is poisoned over time by the sulfur-containing compound remaining in the raw material that has not been sufficiently removed in the raw material desulfurization device 2.
  • the reformer which has also conventionally used power, is uniformly filled with a reforming catalyst in consideration of heat resistance under high temperature conditions. Specifically, the temperature tends to decrease near the inlet of the catalyst layer on the upstream side of the gas flow of the reforming catalyst, into which the mixed gas of the desulfurized raw material and steam flows, because the steam reforming reaction is an endothermic reaction. On the other hand, thermodynamic equilibrium is restricted near the catalyst layer outlet downstream of the gas flow, so the temperature of the reforming catalyst must be as high as 600 to 700 ° C to obtain high conversion. There is a need. Therefore, a heat-resistant reforming catalyst is used as the conventional reforming catalyst! / Puru.
  • the catalyst carrier itself is a stable one with a low surface area, and the carrier metal constituting the catalyst is relatively large! In many cases, the carrier metal is not being used effectively near the entrance of the catalyst layer, which is not easily affected by sintering due to high heat.
  • the larger the number of catalytic active points of Ru as the catalyst metal the larger the amount of adsorbed sulfur-adsorbed compound becomes. It means that it is packed with a weak reforming catalyst.
  • the unit volume becomes lower than the Ru-based reforming catalyst 22 on the downstream side of the gas flow in a portion near the inlet of the catalyst layer, which is lower in temperature and hardly affected by sintering.
  • the number of catalyst active points is large, and the Ru-based reforming catalyst 21 on the upstream side of the gas flow is filled.
  • the above-mentioned portion is filled with the Ru-based reforming catalyst 21 on the gas flow upstream side having a larger surface area per unit volume (BET surface area) than the Ru-based reforming catalyst 22 on the downstream side of the gas flow.
  • the above portion is filled with the Ru-based reforming catalyst 21 on the upstream side of the gas flow having a larger content of the catalytic metal per unit volume than the Ru-based reforming catalyst 22 on the downstream side of the gas flow.
  • the gas flow having a smaller average particle diameter of the catalyst metal than the Ru-based reforming catalyst 22 on the downstream side of the gas flow
  • the upstream side Ru-based reforming catalyst 21 is filled.
  • the reforming catalyst 103 is configured so that the catalytic activity against sulfur poisoning is hardly reduced (see FIG. 2).
  • the operating temperature of the Ru-based reforming catalyst 21 on the upstream side of the gas flow is set to 500 ° C or lower, and the operating temperature of the Ru-based reforming catalyst 22 on the downstream side of the gas flow is set to 700 ° C or lower. , Each has been set.
  • the reformed gas generated in the reformer 5 slightly changes depending on the temperature of the reforming catalyst 103, but as an average value excluding steam, about 80% of hydrogen, carbon dioxide, Each contains about 10% of carbon oxide. Therefore, the CO content of the reformed gas generated in the reformer 5 is reduced to about 0.5% by the shift reaction in the shift converter 6 installed downstream of the reformer 5. Further, in the purifier 7 installed on the downstream side of the transformer 6, oxygen in the air supplied from the air supplier 8 is chemically reacted with CO, so that the CO concentration in the reformed gas is increased. To less than 10 ppm. As a result, the reformed gas is purified into a high-quality reformed gas rich in hydrogen that can be supplied to the PEFC.
  • the reformed gas thus obtained is supplied to the fuel electrode side of the fuel cell 9.
  • the air humidified by the air supply device 16 and the heat exchanger 11 is supplied to the air electrode side of the fuel cell 9.
  • the fuel cell 9 generates power so as to output power.
  • the fuel cell 9 is cooled by the cooling water supplied by the cooling water circulating device 10 so as to be within a predetermined temperature range.
  • the temperature of the cooling water flowing in the fuel cell 9 is detected by a cooling water temperature detector 12.
  • the cooling water circulating device 10 is controlled to increase or decrease the amount of cooling water circulated so that the temperature of the cooling water detected by the cooling water temperature detector 12 becomes substantially constant. It is controlled to be within the temperature range.
  • the reformed gas (off-gas) and air that are exhausted from the fuel cell 9 and are not used for power generation are introduced into the condenser 13. Then, in the condensing device 13, the moisture contained in the reformed gas and the air is condensed by a predetermined condensing mechanism. Thereby, off-gas and air are dehumidified.
  • the dehumidified off-gas is supplied to the reforming heater 17 in the hydrogen generator 101.
  • the dehumidified air is released into the atmosphere.
  • the water condensed by the condensing device 13 into a liquid state is supplied to the water purification device. After being purified by the ion exchange resin of the device 14, it is returned to the water tank 15.
  • the water returned to the water tank 15 is supplied again to the evaporator 4 by the reformed water supply device 3.
  • the power generation operation is continuously performed.
  • the operation of the fuel cell system 100 is appropriately controlled by a control device not particularly shown in FIG.
  • the reforming catalyst 103 is filled with a Ru-based reforming catalyst 21 containing 0.03 g of Ru, which has a larger number of catalytically active points per unit volume, as the Ru-based reforming catalyst 21.
  • a Ru-based reforming catalyst 22 is filled with a reforming catalyst containing 0.1 Olg / cc of Ru having a smaller number of catalytic active points per unit volume. Further, regarding the volume ratio, the Ru-based reforming catalyst 21 is 3 and the Ru-based reforming catalyst 22 is 7.
  • the composition of city gas in which methane is 88.9% by volume, ethane is 6.8% by volume, propane is 3.1% by volume, and butane is 1.2% by volume is simulated.
  • the fuel used was mixed with nitrogen containing general (CH) CSH as an odorant component.
  • the concentration of the odorant in the food was adjusted to be lOOppb, and an acceleration test on the transfer ratio was performed.o
  • a Ru-based reforming catalyst 21 was set to 3 and a Ru-based reforming catalyst 22 was set to 7 by filling a reforming catalyst containing more Ru with 0.03 g of Zcc. After the operation, it was found that the transfer ratio decreased to 75% or less. This is because the Ru-based reforming catalyst 21 filled on the downstream side of the gas flow had a sufficient capacity to adsorb the sulfur-containing compound of the Ru-based reforming catalyst filled on the upstream side of the gas flow. This is probably because the catalytic activity of the catalyst 22 was not maintained.
  • the volume ratio between the Ru-based reforming catalyst 21 and the Ru-based reforming catalyst 22 is described.
  • the force described in the embodiment in which the Ru-based reforming catalyst 21 is 3 and the Ru-based reforming catalyst 22 is 7 is not limited to this embodiment.
  • the catalyst is charged so that the operating time, the fuel flow rate, and the amount of the sulfur-containing compound calculated from the sulfur concentration in the fuel assumed as the device can be adsorbed on the upstream side of the gas flow. This makes it possible to maintain the catalyst activity on the downstream side of the gas flow and maintain a predetermined conversion ratio.
  • the reforming catalyst 103 is configured by disposing the Ru-based reforming catalyst 21 on the upstream side of the gas flow and the Ru-based reforming catalyst 22 on the downstream side of the gas flow.
  • the force described above is not limited to this form.
  • various characteristics such as the number of catalytically active points per unit volume, the average particle diameter of the catalytic metal, the surface area per unit volume, and the catalytic metal content per unit volume are as follows.
  • the reforming catalyst 103 may be configured to change stepwise or continuously.
  • the reforming catalyst 103 is divided into a Ru-based reforming catalyst 21 and a Ru-based reforming catalyst 22.
  • the reforming catalyst 103 is composed of a large number of Ru-based reforming catalysts as a dividing mode in which the dividing mode is further subdivided in the direction in which the mixed gas flows (for example, a dividing mode in which the gas is divided into 5 to 10 stages) Examples include the form. Further, as the form in which the various characteristics are continuously changed, the divided form in the step-wise changed form is divided more finely, and the various properties are smoother in the flow direction of the mixed gas. And the like. Even with such a large configuration, it is possible to obtain the same effects as those obtained in the present embodiment.
  • the power of using a pellet-shaped catalyst as the Ru-based reforming catalyst 21 and the Ru-based reforming catalyst 22 is not limited to this.
  • a configuration in which a honeycomb catalyst is used as the system reforming catalyst 22 may be adopted.
  • FIG. 3 is a block diagram schematically showing the configuration of the normal-pressure flow reactor according to Example 1 of the present invention.
  • the normal pressure flow type reaction apparatus 102 includes a water tank 32 for storing water and a water tank.
  • a water supply device 33 for supplying the water stored in the tank 32 to the evaporator 34; an evaporator 34 for converting the water supplied from the water supply device 33 into steam;
  • a gas supply device 31 for supplying a raw material gas, a reforming catalyst 35 for generating a reformed gas using the raw material gas and steam, and a reforming catalyst 35 required for the steam reforming reaction.
  • an electric furnace 36 for heating to a temperature.
  • the water tank 32 and the water supply device 33 are connected by a predetermined pipe.
  • Predetermined pipes extend from the evaporator 34 and the gas supply apparatus 31, and these pipes are unified at predetermined positions to supply a mixed gas of raw material gas and steam to the reforming catalyst 35. It is arranged as possible.
  • FIG. 4 is a correlation diagram showing the result of evaluating the effect of the reaction temperature on the number of catalytically active points of the reforming catalyst according to Example 1 of the present invention.
  • FIG. 5 is a correlation diagram showing the results of evaluating the effect of the reaction temperature on the catalytic activity (methane conversion ratio) of the reforming catalyst according to Example 1 of the present invention.
  • Fig. 5 shows that the Ru-based catalyst A having a large number of catalytically active points has a higher catalytic activity than the Ru-based catalyst B at a temperature of 400 ° C to 500 ° C. In the high temperature range of ⁇ 700 ° C, this indicates that the number of active catalyst points decreases due to sintering and the activity decreases.
  • methane gas was supplied from the gas supply device 31 at a rate of 100 mL / min.
  • the reformed water was supplied from the water tank 32 to the evaporator 34 by the water supply device 33 so that the SZC became 3.
  • a pellet-type Ru-based reforming catalyst was used as the reforming catalyst 35, and 10 mL of this was filled.
  • the Ru-based reforming catalyst a Ru-based catalyst A having a large number of catalytically active points and a Ru-based catalyst B having a small number of catalytically active points were used.
  • the reforming catalyst 35 was heated by the electric furnace 36 so that the temperature of the reforming catalyst 35 became 450 ° C. or 700 ° C. Then, the methane conversion ratio after 100 hours was evaluated.
  • FIG. 6 is a correlation diagram showing the evaluation results regarding sulfur poisoning of the reforming catalyst according to Example 2 of the present invention.
  • FIG. 7 is a block diagram schematically showing a configuration of a second normal-pressure flow reactor according to Embodiment 3 of the present invention.
  • the basic configuration of the normal pressure flow reactor 102 is the same as the configuration of the normal pressure flow reactor 102 shown in FIG.
  • the reforming catalyst is constituted by the reforming catalyst 35a on the upstream side of the gas flow and the reforming catalyst 35b on the downstream side of the gas flow.
  • the other components have the same configuration as the configuration of the normal-pressure flow reactor 102 shown in FIG.
  • ion-exchanged water was used as the reforming water, and the reforming water was supplied from the water tank 32 to the evaporator 34 so that the SZC became 3 from the water tank 32.
  • Test 1 As the reforming catalyst 35a, the number of catalyst active points per unit volume excellent in low-temperature activity was large, 10 mL of pellet-type Ru-based catalyst A, and thermal stability at high temperature as the reforming catalyst 35b. 10 mL of pelletized Ru-based catalyst B, which has a small number of catalytically active points per unit volume, with emphasis on, was used. In Test 2, as the reforming catalyst 35a and the reforming catalyst 35b, 10 mL each of a Ru-based catalyst B having a small number of catalytic active points per unit volume, which emphasizes thermal stability at high temperatures, was used.
  • FIG. 8 is a correlation diagram showing the result of evaluating the effect of the reaction temperature on the catalytic activity (methane conversion) of the reforming catalyst according to Example 3 of the present invention.
  • test 1 having the same configuration as the catalyst configuration shown in the present embodiment was compared with the tests 2 and 3 in comparison with the tests 2 and 3. High rate and longevity I helped to be a life.
  • Ru-based catalyst C and Ru-based catalysts D having different metal particle diameters of supported Ru were prepared.
  • Ru-based catalyst C and Ru-based catalyst D support the same weight percent of Ru, and therefore the number of catalytic active points per unit volume is higher for Ru-based catalyst C than for Ru-based catalyst D. Will also be many.
  • methane gas at a rate of 100 mL / min, and nitrogen containing 1% of (CH) CSH at a rate of 1 mL / min.
  • FIG. 9 is a correlation diagram showing the results of evaluating the effect of the average particle size of the catalyst metal on the catalytic activity (methane conversion) of the reforming catalyst according to Example 4 of the present invention.
  • the surface area of the catalyst body can be increased by using a carrier having a high surface area. Therefore, ⁇ -alumina in the form of pellets with a surface area of 100 m 2 Zcc and a-alumina in the form of pellets with a surface area of 3 m 2 Zcc are used as carriers, respectively, and are impregnated with 0.1 Olg / cc of Ru using an aqueous ruthenium chloride solution.
  • a pellet-type Ru-based catalyst E and a pellet-shaped Ru-based catalyst F were prepared. Using the Ru-based catalyst E and the Ru-based catalyst F, the number of catalytically active points per unit volume and the surface area after Ru loading (BET surface area) were examined. In this study, the BET surface area was measured using BELSORP36 (manufactured by Nippon Bell).
  • FIG. 10 is a correlation diagram showing the number of catalytically active points per unit volume of Ru-based catalyst E and Ru-based catalyst F according to Example 5 of the present invention and the surface area after supporting Ru.
  • the number of catalytically active points is shown as the catalytically active point density.
  • the ⁇ -alumina surface area of 100 m 2 ZCC is Ru-based catalysts E used in the carrier, a surface area of a alumina 3m 2 ZCC compared to Ru-based catalyst F was used as a carrier Therefore, the surface area is large and the catalytic active site density is high.
  • methane gas was supplied from the gas supply device 31 at a rate of 100 mL / min.
  • the reformed water was supplied from the water supply device 33 to the evaporator device 34 from the water tank 32 so that the SZC became 3.
  • FIG. 11 is a correlation diagram showing the results of evaluating the effect of the surface area of the catalyst body on the catalytic activity (methane conversion) of the reforming catalyst according to Example 5 of the present invention.
  • FIG. 12 is a correlation diagram showing the weight percentage of Ru and the number of catalytically active points per unit volume of Ru-based catalyst G and Ru-based catalyst H according to Example 6 of the present invention.
  • the number of catalytically active points is shown as the catalytically active point density.
  • methane gas was supplied from the gas supply device 31 at a rate of 100 mL / min.
  • Nitrogen containing 1% CSH was supplied at a rate of 1 mL / min.
  • the reformed water was supplied from a water tank 32 to an evaporator 34 from a water tank 32 such that the SZC became 3.
  • FIG. 13 is a correlation diagram showing the results of evaluating the effect of the Ru content on the catalytic activity (methane conversion) of the reforming catalyst according to Example 6 of the present invention.
  • the Ru-based catalyst I and the Ru-based catalyst B were prepared by powdering each of the Ru-based catalyst A and the Ru-based catalyst B, and coating the same amount on a 10 mL volume of a honeycomb support made of cordierite. I prepared the touch ⁇ [.
  • Ru-based catalyst I and Ru-based catalyst ⁇ are coated with the same amount of Ru-based catalyst A and Ru-based catalyst B, and the relative values of the number of catalytic active points per unit volume are shown in Fig. 4. This is equivalent to the relative value of the number of active catalyst points.
  • Test 10 as the reforming catalyst 35a, a honeycomb-shaped Ru-based catalyst I having excellent low-temperature activity and having a large number of catalyst active points per unit volume was used, and as the reforming catalyst 35b, thermal stability at high temperatures was used. A honeycomb-shaped Ru-based catalyst J with a small number of catalytically active points per unit volume was used. In Test 11, for both the reforming catalyst 35a and the reforming catalyst 35b, a honeycomb-shaped Ru-based braid having a small number of catalytic active points per unit volume, which emphasized thermal stability at high temperatures, was used.
  • Ru-based catalysts I having excellent low-temperature activity and having a large number of catalytically active points per unit volume were used.
  • the inlet temperature of the reforming catalyst was 435 ° C and the outlet temperature was 670 ° C.
  • FIG. 14 is a correlation diagram showing the results of evaluating the catalytic activity of the reforming catalyst when the honeycomb catalyst according to Example 7 of the present invention was used.
  • Ru-based catalyst B or pelletized a-alumina was used alone or as a mixture as the reforming catalyst 35a and the reforming catalyst 35b.
  • the atmospheric pressure flow reactor 102 shown in FIG. 7 was used to supply methane gas at a rate of 100 mL / min and nitrogen containing 1% of (CH 2) CSH from the gas supply device 31. Every minute 1
  • Each was supplied at a rate of mL.
  • ion-exchanged water was used as the reforming water, and the reforming water was supplied from the water supply device 33 to the evaporator device 34 from the water tank 32 such that the SZC became 3.
  • FIG. 15 is a correlation diagram showing the results of evaluating the catalytic activity of the reforming catalyst when the reforming catalyst according to Example 8 of the present invention was diluted and used.
  • FIG. 16 is a block diagram schematically showing a configuration of a third normal-pressure flow reactor according to Embodiment 9 of the present invention.
  • the basic configuration of the normal pressure flow type reaction apparatus is the same as the configuration of the normal pressure flow type reaction apparatus 102 shown in FIG.
  • the other components have the same configuration as the configuration of the normal pressure flow reactor 102 shown in FIG.
  • Ru-based catalyst B or pellet-shaped a-alumina was used alone or as a mixture as the reforming catalysts 35a to 35d.
  • Each was supplied at a rate of 1 mL. Also, use ion-exchanged water as the reforming water. Then, the reformed water was supplied from the water supply device 33 to the evaporator 34 so that the SZC became 3.
  • a reforming catalyst obtained by mixing 2 mL of Ru-based catalyst B and 3 mL of a-alumina was used as the reforming catalyst 35a, and 3 mL of Ru-based catalyst B and a-alumina were used as the reforming catalyst 35b.
  • a reforming catalyst mixed with 2 mL using a reforming catalyst obtained by mixing 4 mL of Ru-based catalyst B and 1 mL of a-alumina as reforming catalyst 35c, and 5 mL of Ru-based catalyst B as reforming catalyst 35d Using.
  • the inlet temperature of the reforming catalyst was 430 ° C and the outlet temperature was 685 ° C.
  • the inlet temperature of the reforming catalyst was 440 ° C and the outlet temperature was 660. C.
  • FIG. 17 is a correlation diagram showing the results of evaluating the catalytic activity of the reforming catalyst when the number of stages of the reforming catalyst according to Example 9 of the present invention was increased.
  • the configuration in which the configuration of the reforming catalysts 35a to 35d was applied in the test 15 was smaller than the configuration in the test 16 in the conversion ratio.
  • the same result as in the present embodiment can be obtained by using a technique of diluting the reforming catalyst with an inert substance such as OC-alumina and thereby changing the number of catalytic active points in multiple steps. I was able to help.
  • a method of changing the number of catalytic active points using OC-alumina was exemplified.
  • a method of changing the number of catalytic active points by increasing / decreasing the amount of noble metal carried is easily effective. It can be analogized to
  • the number of catalytically active points was determined by a CO pulse measurement method generally used as a method for evaluating physical properties of a catalyst.
  • the details of this CO pulse measurement method are described in the “Guide to Use of Reference Catalysts, List of Reference Catalyst References, and Manual for Standardization of Measurement Methods” by the Reference Catalyst Committee of the Japan Catalysis Society, published in August 1998. ing.
  • the reforming catalyst was reduced in a stream of hydrogen at 400 ° C, and then allowed to cool.
  • the adsorption amount of carbon monoxide was determined using a measuring device using TCD as a detector with helium as the gas. Then, on the assumption that one molecule of carbon monoxide was adsorbed on one metal particle, the number of catalytically active points of the catalytic metal was determined, and thereby the density of catalytically active points was determined.
  • the particle diameter D of the catalyst metal was calculated as follows.
  • the total surface area S of the supported catalyst metal per unit volume is, assuming that the lattice constant of the supported catalyst metal is a, one carbon monoxide molecule per square of a If the number of molecules of carbon monoxide adsorbed on a unit volume of catalyst metal is assumed to be K mole, it can be expressed as in equation (2).
  • the effective surface area S of one catalytic metal particle can be expressed as in Equation (3).
  • the volume V of one catalytic metal particle can be expressed as in equation (4).
  • the total volume V of the supported catalyst metal particles can be expressed as in Equation (6).
  • the total volume V of the supported catalyst metal particles can be expressed as in equation (7). it can.
  • the particle diameter D of the catalyst metal is derived as in equation (8).
  • d and Si can be calculated by the equations (2) and (7) using the values of F, d, a, and K, so that the particle diameter D of the catalyst metal is obtained. It becomes possible.
  • the hydrogen generator and the fuel cell system according to the present invention improve the conversion rate of the fuel raw material to hydrogen, and exhibit a stable operation with a large sulfur adsorption capacity and a long life.

Landscapes

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

Il est prévu un appareil de production d’hydrogène comprenant un reformeur (5) pour obtenir un gaz reformé contenant de l’hydrogène par une réaction de reformation utilisant au moins un gaz mélangé comprenant un matériau de départ d’hydrocarbure et de l’eau, un lit catalytique de reformation (103) pour permettre au gaz de mélange de passer à travers celui-ci dans le reformeur et pour permettre la réaction de reformation du gaz de mélange, et un radiateur (17) pour chauffer le lit catalytique de reformation pour la réaction de reformation. Le nombre de sites actifs catalytiques par volume unitaire dans une partie d’écoulement d’arrivée de gaz de mélange dans le lit catalytique de reformation est plus grand que le nombre de sites actifs catalytiques par volume unitaire dans une partie d’écoulement de sortie de gaz de mélange dans le lit catalytique de reformation.
PCT/JP2005/009553 2004-05-25 2005-05-25 Appareil de production d’hydrogène et système à cellule électrochimique utilisant l’appareil Ceased WO2005115912A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-155058 2004-05-25
JP2004155058 2004-05-25

Publications (1)

Publication Number Publication Date
WO2005115912A1 true WO2005115912A1 (fr) 2005-12-08

Family

ID=35450786

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/009553 Ceased WO2005115912A1 (fr) 2004-05-25 2005-05-25 Appareil de production d’hydrogène et système à cellule électrochimique utilisant l’appareil

Country Status (1)

Country Link
WO (1) WO2005115912A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101573290B (zh) * 2006-11-08 2012-05-30 出光兴产株式会社 改质器、改质单元及燃料电池系统
WO2013042314A1 (fr) * 2011-09-22 2013-03-28 パナソニック株式会社 Procédé de production de gaz contenant de l'hydrogène et procédé pour le fonctionnement d'un système pile à combustible
US9090563B2 (en) 2004-07-23 2015-07-28 Endocyte, Inc. Bivalent linkers and conjugates thereof
US9138484B2 (en) 2007-06-25 2015-09-22 Endocyte, Inc. Conjugates containing hydrophilic spacer linkers
US9505747B2 (en) 2012-03-29 2016-11-29 Endocyte, Inc. Processes for preparing tubulysin derivatives and conjugates thereof
US9555139B2 (en) 2007-03-14 2017-01-31 Endocyte, Inc. Binding ligand linked drug delivery conjugates of tubulysins
US9662402B2 (en) 2012-10-16 2017-05-30 Endocyte, Inc. Drug delivery conjugates containing unnatural amino acids and methods for using
US9877965B2 (en) 2007-06-25 2018-01-30 Endocyte, Inc. Vitamin receptor drug delivery conjugates for treating inflammation
US10080805B2 (en) 2012-02-24 2018-09-25 Purdue Research Foundation Cholecystokinin B receptor targeting for imaging and therapy

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0380102A (ja) * 1989-08-21 1991-04-04 Toshiba Corp 燃料改質装置
JPH04243539A (ja) * 1991-01-24 1992-08-31 Fuji Electric Co Ltd 燃料改質器
JPH0867502A (ja) * 1994-08-30 1996-03-12 Ngk Insulators Ltd 燃料改質装置
JPH09309702A (ja) * 1996-05-22 1997-12-02 Osaka Gas Co Ltd 燃料電池用の燃料改質器
JP2000007304A (ja) * 1998-06-29 2000-01-11 Ngk Insulators Ltd 改質反応装置
JP2002308604A (ja) * 2001-04-10 2002-10-23 Toyota Motor Corp 燃料改質装置
JP2003221208A (ja) * 2002-01-29 2003-08-05 Nissan Motor Co Ltd アルマイト触媒を用いてなる反応装置
JP2004067454A (ja) * 2002-08-07 2004-03-04 Toyota Motor Corp 燃料改質装置および水素生成方法
JP6088761B2 (ja) * 2012-07-30 2017-03-01 国立大学法人佐賀大学 臓器測定装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0380102A (ja) * 1989-08-21 1991-04-04 Toshiba Corp 燃料改質装置
JPH04243539A (ja) * 1991-01-24 1992-08-31 Fuji Electric Co Ltd 燃料改質器
JPH0867502A (ja) * 1994-08-30 1996-03-12 Ngk Insulators Ltd 燃料改質装置
JPH09309702A (ja) * 1996-05-22 1997-12-02 Osaka Gas Co Ltd 燃料電池用の燃料改質器
JP2000007304A (ja) * 1998-06-29 2000-01-11 Ngk Insulators Ltd 改質反応装置
JP2002308604A (ja) * 2001-04-10 2002-10-23 Toyota Motor Corp 燃料改質装置
JP2003221208A (ja) * 2002-01-29 2003-08-05 Nissan Motor Co Ltd アルマイト触媒を用いてなる反応装置
JP2004067454A (ja) * 2002-08-07 2004-03-04 Toyota Motor Corp 燃料改質装置および水素生成方法
JP6088761B2 (ja) * 2012-07-30 2017-03-01 国立大学法人佐賀大学 臓器測定装置

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9550734B2 (en) 2004-07-23 2017-01-24 Endocyte, Inc. Bivalent linkers and conjugates thereof
US9090563B2 (en) 2004-07-23 2015-07-28 Endocyte, Inc. Bivalent linkers and conjugates thereof
US10647676B2 (en) 2004-07-23 2020-05-12 Endocyte, Inc. Bivalent linkers and conjugates thereof
CN101573290B (zh) * 2006-11-08 2012-05-30 出光兴产株式会社 改质器、改质单元及燃料电池系统
US9555139B2 (en) 2007-03-14 2017-01-31 Endocyte, Inc. Binding ligand linked drug delivery conjugates of tubulysins
US10738086B2 (en) 2007-06-25 2020-08-11 Endocyte Inc. Conjugates containing hydrophilic spacer linkers
US9877965B2 (en) 2007-06-25 2018-01-30 Endocyte, Inc. Vitamin receptor drug delivery conjugates for treating inflammation
US10500204B2 (en) 2007-06-25 2019-12-10 Endocyte, Inc. Vitamin receptor drug delivery conjugates for treating inflammation
US9138484B2 (en) 2007-06-25 2015-09-22 Endocyte, Inc. Conjugates containing hydrophilic spacer linkers
WO2013042314A1 (fr) * 2011-09-22 2013-03-28 パナソニック株式会社 Procédé de production de gaz contenant de l'hydrogène et procédé pour le fonctionnement d'un système pile à combustible
US10080805B2 (en) 2012-02-24 2018-09-25 Purdue Research Foundation Cholecystokinin B receptor targeting for imaging and therapy
US10765756B2 (en) 2012-02-24 2020-09-08 Purdue Research Foundation Cholecystokinin B receptor targeting for imaging and therapy
US11344623B2 (en) 2012-02-24 2022-05-31 Purdue Research Foundation Cholecystokinin B receptor targeting for imaging and therapy
US12485179B2 (en) 2012-02-24 2025-12-02 Purdue Research Foundation Cholecystokinin B receptor targeting for imaging and therapy
US9505747B2 (en) 2012-03-29 2016-11-29 Endocyte, Inc. Processes for preparing tubulysin derivatives and conjugates thereof
US9662402B2 (en) 2012-10-16 2017-05-30 Endocyte, Inc. Drug delivery conjugates containing unnatural amino acids and methods for using

Similar Documents

Publication Publication Date Title
KR101357431B1 (ko) 수소제조장치 및 연료전지 시스템과 그 운전방법
JP5121533B2 (ja) 水素製造装置、およびそれを用いた燃料電池システム
JP7485882B2 (ja) 水素生成装置およびそれを用いた燃料電池システム並びにその運転方法
WO2000048261A1 (fr) Convertisseur de co et systeme de production pour pile a combustible
KR20030040391A (ko) 일산화탄소 제거 촉매의 활성화 방법, 일산화탄소 제거촉매, 일산화탄소 제거 방법, 및 연료 전지 시스템의 운전방법
JP2004284875A (ja) 水素製造システムおよび燃料電池システム
Maeda et al. Performance of Pt-Fe/mordenite monolithic catalysts for preferential oxidation of carbon monoxide in a reformate gas for PEFCs
US9527055B2 (en) Hydrogen generator and fuel cell system
WO2005115912A1 (fr) Appareil de production d’hydrogène et système à cellule électrochimique utilisant l’appareil
CA2390727A1 (fr) Methode de preparation d'un reformat gazeux a faible teneur en soufre pouvant etre utilise dans un systeme de piles a combustible
US20040241509A1 (en) Hydrogen generator and fuel cell system
JP2006036616A (ja) ゼオライトの製造方法及び該ゼオライトを含む硫黄化合物除去用吸着剤
JP3733753B2 (ja) 水素精製装置
KR20090065444A (ko) 일산화탄소를 선택적으로 산화하는 촉매, 일산화탄소 농도를 저감시키는 방법 및 연료 전지 시스템
JP2006076802A (ja) 水素生成装置およびこれを備えた燃料電池システム並びに水素生成方法
JP2017159290A (ja) 脱硫方法および脱硫装置および燃料電池発電システム
JP2005034682A (ja) Ｃｏ変成触媒およびその製造方法
KR102123871B1 (ko) 스팀 개질을 위한 시스템 및 방법
JP2006167501A (ja) 改質触媒、水素生成装置および燃料電池システム
JP2007210835A (ja) 水素生成装置及び燃料電池システム
JP2014184394A (ja) 水蒸気改質用触媒、改質器、および燃料電池システム
JP4820106B2 (ja) Ｃｏ選択酸化触媒の還元方法
JP2006277980A (ja) 燃料電池用燃料の脱硫方法
JP2005082436A (ja) 水素生成装置およびそれを用いた燃料電池システム
JP2005082409A (ja) 水素生成装置

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP