WO2012090837A1 - Système de désulfuration pour pile à combustible, système de production d'hydrogène pour pile à combustible, système à pile à combustible et procédé de désulfuration pour hydrocarbure - Google Patents

Système de désulfuration pour pile à combustible, système de production d'hydrogène pour pile à combustible, système à pile à combustible et procédé de désulfuration pour hydrocarbure Download PDF

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WO2012090837A1
WO2012090837A1 PCT/JP2011/079719 JP2011079719W WO2012090837A1 WO 2012090837 A1 WO2012090837 A1 WO 2012090837A1 JP 2011079719 W JP2011079719 W JP 2011079719W WO 2012090837 A1 WO2012090837 A1 WO 2012090837A1
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fuel
desulfurization
hydrocarbon
fuel cell
catalyst
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PCT/JP2011/079719
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English (en)
Japanese (ja)
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康嗣 橋本
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Ｊｘ日鉱日石エネルギー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/123—X-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • 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
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    • C01—INORGANIC CHEMISTRY
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    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1029—Catalysts in the form of a foam
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a fuel cell desulfurization system, a fuel cell hydrogen production system, a fuel cell system, and a hydrocarbon fuel desulfurization method.
  • a gas containing hydrogen as a main component is used as a fuel gas for a fuel cell, and a hydrocarbon-based fuel such as natural gas, LPG, naphtha, or kerosene is used as a raw material.
  • hydrocarbon fuels containing carbon and hydrogen are treated at high temperature on a catalyst together with steam, partially oxidized with an oxygen-containing gas, or subjected to a self-heat recovery type reforming reaction in a system where steam and oxygen-containing gas coexist.
  • Hydrogen obtained by the above is used as fuel hydrogen for fuel cells.
  • the catalyst used for the fuel reforming until the production of fuel hydrogen for the fuel cell, the subsequent carbon monoxide removal, and the cathode electrode is used in a reduced state such as noble metal or copper. There are many. In such a state, sulfur acts as a catalyst poison, and there is a problem that the catalytic activity of the hydrogen production process or the battery itself is lowered, and the efficiency is lowered.
  • the hydrocarbon-based fuel that is a raw material for fuel hydrogen in a fuel cell may contain various impurities in addition to sulfur.
  • city gas may contain water that is a temporary poison for the desulfurization agent. When the amount of water in the gas becomes high, the performance of the desulfurizing agent is temporarily lowered, and sulfur is not sufficiently removed.
  • Impurities mixed in hydrocarbon fuels vary in type and concentration, making it difficult to deal with poisons of desulfurization agents.
  • the present invention relates to a highly durable fuel cell desulfurization system and hydrogen production system capable of maintaining a desired desulfurization performance for a long period of time even when a hydrocarbon fuel containing a desulfurization agent poison is supplied. It is another object of the present invention to provide a fuel cell system and a hydrocarbon fuel desulfurization method.
  • a desulfurization system for a fuel cell is a desulfurization system for a fuel cell for removing a sulfur compound from a circulating hydrocarbon fuel containing a sulfur compound.
  • a desulfurization section is provided, and the desulfurization section is composed of a plurality of zeolites carrying active metals at different concentrations, and the plurality of zeolites has a high active metal concentration from the upstream side to the downstream side in the flow direction of the hydrocarbon fuel.
  • a desulfurizing agent arranged in the order of lower.
  • a hydrocarbon is provided even when a hydrocarbon-based fuel containing a desulfurization agent poison is supplied by providing the desulfurization unit having the above-described configuration.
  • the sulfur compound contained in the system fuel can be sufficiently removed over a long period of time.
  • the present inventors can adsorb the poisonous substance by the zeolite in which the active metal disposed upstream is supported at a high concentration, and the activity of the zeolite catalyst disposed thereafter is sufficiently maintained. It is thought that it is possible to suppress the sulfur from slipping to the subsequent stage.
  • the zeolite may be X-type zeolite or Y-type zeolite, and the active metal may be Ag or Cu.
  • the hydrocarbon fuel can contain a hydrocarbon compound having 4 or less carbon atoms.
  • the fuel cell desulfurization system further includes a fuel supply unit that supplies 0.001 to 2% by volume of water at 25 ° C. and supplies a hydrocarbon-based fuel containing a sulfur compound to the desulfurization unit. be able to.
  • the moisture content as used in this specification is the value which converted the dew point temperature measured with the dew point meter into the moisture content in 25 degreeC.
  • a fuel cell hydrogen production system includes a fuel cell desulfurization system according to one aspect of the present invention and hydrogen that generates hydrogen from a hydrocarbon-based fuel that has passed through a desulfurization section of the fuel cell desulfurization system.
  • a generator is
  • the fuel cell desulfurization system according to one aspect of the present invention is provided, so that the hydrocarbon fuel containing the desulfurization agent poisonous substance is supplied.
  • the sulfur compound from flowing into the hydrogen generating portion over a long period of time, and thereby it is possible to sufficiently maintain the hydrogen production efficiency over a long period of time.
  • a fuel cell system according to one aspect of the present invention includes a fuel cell hydrogen production system according to one aspect of the present invention.
  • Fuel hydrogen can be stably supplied to the cathode of the fuel cell, and the power generation efficiency can be sufficiently maintained over a long period of time.
  • a hydrocarbon-based fuel containing a sulfur compound is circulated in descending order of the active metal concentration of a plurality of zeolites carrying active metals at different concentrations.
  • the sulfur compound in the hydrocarbon-based fuel is sufficiently removed over a long period of time. Can be removed.
  • the zeolite may be X-type zeolite or Y-type zeolite, and the active metal may be Ag or Cu.
  • the hydrocarbon fuel can contain a hydrocarbon compound having 4 or less carbon atoms.
  • the hydrocarbon fuel can contain 0.001 to 2% by volume of water at 25 ° C. According to the hydrocarbon-based fuel desulfurization method of the present invention, desulfurization can be stably performed over a long period of time even when a hydrocarbon-based fuel containing water in the above proportion is desulfurized.
  • a highly durable fuel cell desulfurization system capable of maintaining a desired desulfurization performance for a longer period of time even when a hydrocarbon-based fuel containing a desulfurization agent poison is supplied, hydrogen A manufacturing system, a fuel cell system, and a hydrocarbon-based fuel desulfurization method can be provided.
  • FIG. 1 is a conceptual diagram showing an example of a fuel cell system according to an embodiment of the present invention.
  • the fuel cell system 1 includes a fuel supply unit 2, a desulfurization unit 3, a hydrogen generation unit 4, a cell stack 5, an off-gas combustion unit 6, a water supply unit 7, a water vaporization unit 8, and an oxidant supply unit. 9, a power conditioner 10, and a control unit 11.
  • Each part is connected by piping (not shown) in the flow shown in FIG.
  • the fuel supply unit 2 and the desulfurization unit 3 constitute a fuel cell desulfurization system 20.
  • the fuel supply unit 2 supplies hydrocarbon fuel to the desulfurization unit 3.
  • hydrocarbon fuels include hydrocarbons, alcohols, ethers, and biofuels. These hydrocarbon fuels are derived from conventional fossil fuels such as petroleum and coal, and synthesized from syngas. A fuel-derived one or a biomass-derived one can be used as appropriate. Specific examples of hydrocarbons include methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, town gas, gasoline, naphtha, kerosene, and light oil.
  • Examples of alcohols include methanol and ethanol.
  • Examples of ethers include dimethyl ether.
  • Biofuels include biogas, bioethanol, biodiesel, and biojet.
  • a gas containing methane as a main component for example, city gas, town gas, natural gas, biogas, etc.
  • LPG supplied through a pipeline is suitable. Can be used for
  • the desulfurization section 3 When using hydrocarbon fuel supplied from a pipeline, there is a possibility that temporary poisons such as moisture may be mixed due to damage to the pipeline. According to the desulfurization section 3 according to the present invention, even when such a hydrocarbon fuel is supplied, the desulfurization performance is maintained over a longer period than the desulfurization section not having the configuration according to the present invention. It becomes possible to do.
  • the hydrocarbon fuel contains a hydrocarbon compound having 4 or less carbon atoms.
  • the hydrocarbon compound having 4 or less carbon atoms include saturated aliphatic hydrocarbons such as methane, ethane, propane, and butane, and unsaturated aliphatic hydrocarbons such as ethylene, propylene, and butene.
  • the hydrocarbon-based fuel is preferably a gas containing a hydrocarbon compound having 4 or less carbon atoms, that is, a gas containing one or more of methane, ethane, ethylene, propane, propylene, butane and butene.
  • gas containing a C4 or less hydrocarbon compound the gas containing 80 volume% or more of methane is preferable, and the gas containing 85 volume% or more of methane is more preferable.
  • the hydrocarbon fuel generally contains a sulfur compound.
  • the sulfur compound include sulfur compounds originally mixed in hydrocarbons and the like, and compounds contained in odorants for detecting gas leaks.
  • sulfur compounds originally mixed in hydrocarbons include hydrogen sulfide (H 2 S), carbonyl sulfide (COS), carbon disulfide (CS 2 ), and the like.
  • As the odorant alkyl sulfide, mercaptan alone or a mixture thereof is used.
  • DES diethyl sulfide
  • DMS dimethyl sulfide
  • EMS ethyl methyl sulfide
  • TBM tert-butyl mercaptan
  • isopropyl mercaptan dimethyl disulfide (DMDS), diethyl disulfide (DEDS) and the like
  • the sulfur compound is contained in an amount of about 0.1 to 10 ppm by mass in terms of sulfur atom based on the total amount of hydrocarbon fuel.
  • Hydrocarbon fuels may contain substances that poison active metals such as moisture and carbon monoxide as desulfurizing agents.
  • active metals such as moisture and carbon monoxide as desulfurizing agents.
  • the hydrocarbon fuel contains water, it can contain 0.001 to 2% by volume of water at 25 ° C.
  • the desulfurization system according to the present invention including the desulfurization section 3 is constructed, long-term desulfurization performance can be achieved even when using hydrocarbon fuels containing poisonous substances and sulfur compounds as described above. Can be maintained over time.
  • the desulfurization section 3 is composed of a plurality of zeolites supporting active metals at different concentrations, and the plurality of zeolites are from those having a high active metal concentration to a downstream from the upstream side to the downstream side in the flow direction of the hydrocarbon fuel.
  • the desulfurizing agent is arranged in the order as follows.
  • FIG. 2 is a schematic diagram illustrating an example of a desulfurization system according to the present embodiment.
  • the desulfurization unit 3a has a desulfurization agent that is formed by laminating three catalyst layers 101, 102, and 103 including zeolite supporting an active metal.
  • the arrow A indicates the upstream side in the hydrocarbon fuel flow direction
  • the arrow B indicates the downstream side.
  • the catalyst layer 101 contains zeolite having active metal supported at the highest concentration, and the active metal concentration decreases in the order of the catalyst layers 102 and 103.
  • the desulfurization part 3 can be prepared by preparing a plurality of zeolites having different concentrations of the supported active metal and filling them in a predetermined container in order from the lowest or highest active metal concentration.
  • the layer containing the zeolite having the highest concentration of the active metal is disposed on the upstream side in the flow direction of the hydrocarbon fuel.
  • the number of catalyst layers is not particularly limited, but 3 to 7 layers are preferable from the viewpoint of improving desulfurization tax performance and cost.
  • Zeolite includes X-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 2.7 to 3, Y-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 4.5 to 5, and SiO 2 / Al 2 O 3 mol.
  • Examples thereof include mordenite type zeolite having a ratio of 20 to 22.
  • X-type zeolite and Y-type zeolite are preferable in terms of desulfurization performance.
  • Active metals include Ag, Cu, and Zn. Among these, Ag and Cu are preferable in terms of desulfurization performance.
  • the range of the supported amount of copper is preferably 3 to 20% by mass, more preferably 5 to 15% by mass on the basis of zeolite from the viewpoint of improving the desulfurization performance.
  • an ion exchange method is preferably used.
  • the zeolite used for ion exchange various types such as sodium type, ammonium type and proton type can be used, and the sodium type is most preferably used.
  • copper is usually prepared as a cation dissolved in water. Specific examples thereof include aqueous solutions of copper sulfate, copper nitrate, copper chloride, and copper acetate, and aqueous solutions of copper complex ions such as copper ammine complex ions.
  • the concentration of the aqueous solution containing copper ions is usually in the range of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, as the concentration of copper.
  • the ion exchange method is not particularly limited.
  • the above-mentioned zeolite is added to the above-mentioned solution containing cationic copper, and the temperature is usually 0 to 90 ° C., preferably 20 to 70 ° C. for 1 hour to
  • the ion exchange treatment is performed for several hours, preferably with stirring.
  • the solid matter is separated by means such as filtration, washed with water, and then dried at a temperature of 50 to 200 ° C., preferably 80 to 150 ° C.
  • This ion exchange treatment can be repeated.
  • a baking treatment may be performed at 200 to 600 ° C., preferably 300 to 500 ° C. for about several hours.
  • the zeolite supporting copper produced by the above method is made by extrusion molding, tableting molding, rolling granulation, spraying using alumina, silica, clay mineral, etc., or a precursor thereof such as boehmite as an appropriate binder. It can be molded and used in a conventional manner such as drying and firing as necessary. In addition, it is also preferable to preliminarily mold the zeolite and then apply the ion exchange method.
  • the range of silver loading is preferably 10 to 30% by mass, more preferably 15 to 25% by mass on the basis of zeolite from the viewpoint of improving the desulfurization performance.
  • An ion exchange method is preferably used as the silver support method.
  • the zeolite used for ion exchange various types such as sodium type, ammonium type and proton type can be used, and the sodium type is most preferably used.
  • silver is usually prepared as a cation dissolved in water. Specific examples thereof include an aqueous solution of silver nitrate and silver perchlorate, an aqueous solution of silver ammine complex ion, and the like, and an aqueous silver nitrate solution is most preferably used.
  • the concentration of the aqueous solution containing silver ions is usually in the range of 0.5 to 10% by mass, preferably 1 to 5% by mass, as the concentration of silver.
  • the ion exchange method is not particularly limited.
  • the above-mentioned zeolite is added to the above-mentioned solution containing cationic silver, and it is usually 0 to 90 ° C., preferably 20 to 70 ° C. for 1 hour to
  • the ion exchange treatment is performed for several hours, preferably with stirring.
  • the solid matter is separated by means such as filtration, washed with water, and then dried at a temperature of 50 to 200 ° C., preferably 80 to 150 ° C.
  • This ion exchange treatment can be repeated.
  • it may be baked at 200 to 600 ° C., preferably 250 to 400 ° C. for about several hours.
  • the target silver ion exchange zeolite can be obtained.
  • Zeolite carrying silver produced by the above method is alumina, silica, clay mineral, etc., using these precursors such as boehmite as an appropriate binder, extrusion molding, tableting molding, rolling granulation, It can be molded and used by a normal method such as spray drying and firing as necessary. In addition, it is also preferable to pre-mold zeolite and apply the above ion exchange method thereafter.
  • the desulfurization temperature is preferably 100 ° C. or less, for example, in the range of ⁇ 50 ° C. to 100 ° C., more preferably in the range of ⁇ 20 ° C. to 80 ° C., further preferably in the range of 0 to 60 ° C., and still more preferably in the range of 10 to 50 ° C. Selected by range.
  • the gas space velocity GHSV (Gas Hourly Space Velocity) is selected between 10 and 20000 h ⁇ 1 , preferably between 10 and 7000 h ⁇ 1 .
  • GHSV Gas Hourly Space Velocity
  • a liquid space velocity LHSV Liquid Hourly Space Velocity
  • the pressure condition is usually selected in the range of normal pressure to 1 MPa (gauge pressure, the same shall apply hereinafter), preferably normal pressure to 0.5 MPa, more preferably normal pressure to 0.2 MPa. Most preferred.
  • the hydrocarbon fuel from which the sulfur content has been removed by the desulfurization unit 3 is supplied to the hydrogen generation unit 4.
  • the hydrogen generator 4 and the desulfurization system 20 constitute a hydrogen production system 30.
  • the hydrogen generator 4 includes a reformer that reforms the hydrocarbon-based fuel after desulfurization using a reforming catalyst, and generates a hydrogen-rich gas.
  • the reforming method in the hydrogen generating unit 4 is not particularly limited, and for example, steam reforming, partial oxidation reforming, autothermal reforming, and other reforming methods can be employed.
  • the reforming temperature is usually 200 to 800 ° C., preferably 300 to 700 ° C.
  • the hydrogen generator 4 may have a configuration for adjusting the properties in addition to the reformer reformed by the reforming catalyst depending on the properties of the hydrogen rich gas required by the cell stack 5.
  • the hydrogen generating unit 4 is in a hydrogen rich gas. (For example, shift reaction part, selective oxidation reaction part) for removing carbon monoxide.
  • the hydrogen generation unit 4 supplies a hydrogen rich gas to the anode 12 of the cell stack 5.
  • Examples of the reforming catalyst include cerium oxide or a catalyst carrier containing a rare earth element oxide mainly composed of cerium oxide and an active metal supported on the carrier.
  • the supported amount of Ru or Rh is such that the atomic ratio of cerium to Ru or Rh (Ce / Ru or Ce / Rh) is 1 to 250, preferably 2 to 100, more preferably 3 to 50. When the atomic ratio is out of the above range, sufficient catalytic activity may not be obtained, which is not preferable.
  • the supported amount of Ru or Rh is 0.1 to 3.0% by mass, preferably 0.5 to 3.0% by weight, based on the catalyst weight (total weight of catalyst support and active metal), with Ru or Rh as the metal equivalent. 2.5% by mass.
  • the method for supporting Ru or Rh on the catalyst carrier is not particularly limited, and can be easily performed by applying a known method.
  • a known method for example, an impregnation method, a deposition method, a coprecipitation method, a kneading method, an ion exchange method, a pore filling method and the like can be mentioned, and the impregnation method is particularly desirable.
  • the starting material for Ru or Rh used in the production of the catalyst varies depending on the above-mentioned supporting method and can be appropriately selected. Usually, a Ru or Rh chloride or a Ru or Rh nitrate is used.
  • a method of preparing a solution of Ru or Rh salt (usually an aqueous solution), impregnating the carrier, drying, and firing as necessary can be exemplified.
  • the calcination is usually performed in an air or nitrogen atmosphere, and the temperature is not particularly limited as long as it is equal to or higher than the decomposition temperature of the salt, but is usually 200 to 800 ° C, preferably 300 to 800 ° C, more preferably 500. About 800 ° C is desirable.
  • a reducing atmosphere usually a hydrogen atmosphere.
  • the above reforming catalyst may be in a form in which other noble metals (platinum, iridium, palladium, etc.) are further supported.
  • the catalyst carrier of the reforming catalyst is preferably a carrier containing cerium oxide or rare earth element oxide containing cerium oxide as a main component in an amount of 5 to 40% by mass and aluminum oxide in an amount of 60 to 95% by mass.
  • cerium oxide (commonly called ceria) is preferable.
  • the method for preparing cerium oxide is not particularly limited, and for example, cerium nitrate (Ce (NO 3 ) 3 .6H 2 O, Ce (NO 3 ) 4, etc.), cerium chloride (CeCl 3 .nH 2 O) ), Cerium hydroxide (Ce (OH) 3 , Ce (OH) 4 .H 2 O, etc.), cerium carbonate (Ce 2 (CO 3 ) 3 ⁇ 8H 2 O, Ce 2 (CO 3 ) 3 ⁇ 5H 2 O Etc.), cerium oxalate, cerium (IV) ammonium oxalate, cerium chloride and the like as starting materials, and can be prepared by a known method, for example, firing in air.
  • the rare earth element oxide mainly composed of cerium oxide can be prepared from a salt of a mixed rare earth element mainly composed of cerium.
  • the content of cerium oxide is usually 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more.
  • rare earth element oxides other than cerium oxide scandium, yttrium, lanthanum, protheodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc. Is mentioned.
  • oxides of each element of yttrium, lanthanum, and neodymium are preferable, and oxides of lanthanum are particularly preferable.
  • the crystal form is not particularly limited, and any crystal form may be used.
  • Examples of the aluminum oxide include alumina and double oxides of aluminum and other elements such as silicon, copper, iron, and titanium.
  • Typical examples of the double oxide include silica alumina. .
  • alumina is particularly desirable, and the alumina is not particularly limited, and any crystal form such as ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , and ⁇ can be used, and the ⁇ type is particularly preferable.
  • Alumina hydrates such as boehmite, bayerite, and gibbsite can also be used.
  • Silica alumina is not particularly limited, and any crystal form can be used.
  • Aluminum oxide can be used without any problem even if it contains a small amount of impurities.
  • the composition ratio of the cerium oxide and the rare earth element oxide mainly composed of cerium oxide in the catalyst support of the reforming catalyst is preferably 5 to 40% by mass, and more preferably 10 to 35% by mass.
  • the rare earth element oxide containing cerium oxide and cerium oxide as a main component is less than 5% by mass, the carbon precipitation suppressing effect, the activity promoting effect, and the heat resistance improving effect in the presence of oxygen are insufficient, which is not preferable.
  • the amount is more than 40% by mass, the surface area of the support is decreased, and sufficient catalytic activity may not be obtained.
  • the composition ratio of the aluminum oxide in the catalyst carrier of the reforming catalyst is preferably 60 to 95% by mass, and more preferably 65 to 90% by mass.
  • the composition ratio of the aluminum oxide is less than 60% by mass, the surface area of the support is decreased, so that sufficient catalytic activity may not be obtained. This is not preferable because the effect and the effect of improving heat resistance in the presence of oxygen are insufficient.
  • the method for producing the catalyst carrier of the reforming catalyst is not particularly limited, and can be easily produced by a known method.
  • it can be produced by impregnating aluminum oxide with an aqueous solution of cerium or a rare earth element salt containing cerium as a main component, followed by drying and baking.
  • the salt used at this time is preferably a water-soluble salt.
  • Specific examples of the salt include nitrates, chlorides, sulfates, acetates, and the like. Nitrate or organic acid salt is preferable.
  • the calcination is usually performed in air or an oxygen atmosphere, and the temperature is not particularly limited as long as it is equal to or higher than the decomposition temperature of the salt, but it is usually about 500 to 1400 ° C., preferably about 700 to 1200 ° C.
  • the carrier it can also be prepared by a coprecipitation method, a gel kneading method, or a sol-gel method.
  • a catalyst carrier can be obtained in this way, it is preferable to calcinate the catalyst carrier in air or an oxygen atmosphere before supporting Ru or Rh.
  • the firing temperature at this time is usually 500 to 1400 ° C., preferably 700 to 1200 ° C.
  • a small amount of a binder such as silica or cement can be added to the catalyst carrier.
  • the shape of the catalyst carrier of the reforming catalyst is not particularly limited, and can be appropriately selected depending on the form in which the catalyst is used. For example, an arbitrary shape such as a pellet shape, a granule shape, a honeycomb shape, or a sponge shape is adopted.
  • the shape of the reforming catalyst is not particularly limited, and can be appropriately selected depending on the form in which the catalyst is used.
  • an arbitrary shape such as a pellet shape, a granule shape, a honeycomb shape, or a sponge shape is adopted.
  • the water vaporization unit 8 supplies the steam to the hydrogen generation unit 4.
  • the water vapor is preferably generated by heating the water supplied from the water supply unit 7 in the water vaporization unit 8 and vaporizing it. Heating of the water in the water vaporization unit 8 may use heat generated in the fuel cell system 1 such as recovering heat of the hydrogen generation unit 4, heat of the off-gas combustion unit 6, or exhaust gas. Moreover, you may heat water using other heat sources, such as a heater and a burner separately.
  • FIG. 1 only heat supplied from the off-gas combustion unit 6 to the hydrogen generation unit 4 is described as an example, but the present invention is not limited to this.
  • Hydrogen rich gas is supplied from the hydrogen production system 30 to the fuel cell system 1 through a pipe connecting the hydrogen production system 30 and the cell stack 5. Electric power is generated in the cell stack 5 using this hydrogen-rich gas and an oxidizing agent.
  • the type of the cell stack 5 in the fuel cell system 1 is not particularly limited, and examples thereof include a polymer electrolyte fuel cell (PEFC), a solid oxide fuel cell (SOFC), and phosphoric acid.
  • PEFC polymer electrolyte fuel cell
  • SOFC solid oxide fuel cell
  • PAFC Phosphoric Acid Fuel Cell
  • MCFC Molten Carbonate Fuel Cell
  • the components shown in FIG. 1 may be omitted as appropriate according to the type of cell stack 5, the reforming method, and the like.
  • the oxidant is supplied from the oxidant supply unit 9 through a pipe connecting the oxidant supply unit 9 and the fuel cell system 1.
  • the oxidizing agent for example, air, pure oxygen gas (which may contain impurities that are difficult to remove by a normal removal method), or oxygen-enriched air is used.
  • the cell stack 5 generates power using the hydrogen rich gas from the hydrogen generation unit 4 and the oxidant from the oxidant supply unit 9.
  • the cell stack 5 includes an anode 12 to which a hydrogen-rich gas is supplied, a cathode 13 to which an oxidant is supplied, and an electrolyte 14 disposed between the anode 12 and the cathode 13.
  • the cell stack 5 supplies power to the outside via the power conditioner 10.
  • the cell stack 5 supplies the hydrogen rich gas and the oxidant, which have not been used for power generation, to the off gas combustion unit 6 as off gas.
  • a combustion section for example, a combustor that heats the reformer
  • the hydrogen generation section 4 may be shared with the off-gas combustion section 6.
  • the off gas combustion unit 6 burns off gas supplied from the cell stack 5.
  • the heat generated by the off-gas combustion unit 6 is supplied to the hydrogen generation unit 4 and used for generation of a hydrogen rich gas in the hydrogen generation unit 4.
  • the fuel supply unit 2, the water supply unit 7, and the oxidant supply unit 9 are configured by, for example, a pump and are driven based on a control signal from the control unit 11.
  • the power conditioner 10 adjusts the power from the cell stack 5 according to the external power usage state. For example, the power conditioner 10 performs a process of converting a voltage and a process of converting DC power into AC power.
  • the control unit 11 performs control processing for the entire fuel cell system 1.
  • the control unit 11 includes, for example, a device that includes a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), and an input / output interface.
  • the control unit 11 is electrically connected to the fuel supply unit 2, the water supply unit 7, the oxidant supply unit 9, the power conditioner 10, and other sensors and auxiliary equipment not shown.
  • the control unit 11 acquires various signals generated in the fuel cell system 1 and outputs a control signal to each device in the fuel cell system 1.
  • a hydrocarbon-based fuel containing a sulfur compound is circulated in descending order of the active metal concentration of a plurality of zeolites carrying active metals at different concentrations.
  • hydrocarbon fuel containing a sulfur compound examples include the hydrocarbon fuels described above.
  • Specific means for circulating hydrocarbon-based fuels in descending order of the active metal concentration of a plurality of zeolites carrying active metals at different concentrations includes the fuel supply unit 2 and the desulfurization unit 3 described above. . That is, the hydrocarbon fuel is supplied to the desulfurization unit 3 by the fuel supply unit 2, and the hydrocarbon fuel supplied from the fuel supply unit is brought into contact with the desulfurization agent in the desulfurization unit 3.
  • the desulfurization temperature is preferably 100 ° C. or less, for example, in the range of ⁇ 50 ° C. to 100 ° C., more preferably in the range of ⁇ 20 ° C. to 80 ° C., further preferably in the range of 0 to 60 ° C., and still more preferably in the range of 10 to 50. It is selected in the range of ° C.
  • GHSV When using a hydrocarbon-based fuel that is a gas at normal temperature and pressure, such as city gas, GHSV is selected between 10 and 20000 h ⁇ 1 , preferably between 10 and 7000 h ⁇ 1 .
  • GHSV is lower than 10 h ⁇ 1 , the desulfurization performance is sufficient, but since a desulfurizing agent is used more than necessary, the desulfurizer becomes excessively undesirable.
  • GHSV is larger than 20000 h ⁇ 1 , sufficient desulfurization performance cannot be obtained.
  • liquid fuel can also be used as a hydrocarbon-based fuel, and in that case, a range of 0.01 to 100 h ⁇ 1 can be selected as LHSV.
  • the pressure condition is usually selected in the range of normal pressure to 1 MPa (gauge pressure, the same shall apply hereinafter), preferably normal pressure to 0.5 MPa, more preferably normal pressure to 0.2 MPa. Most preferred.
  • Catalyst 2 The catalyst 2 was obtained in the same manner as the catalyst 1 except that the silver nitrate used was changed to 12.7 g and the supported amount of silver was 10% by mass based on the carrier.
  • the catalyst 3 was obtained in the same manner as the catalyst 1 except that the silver nitrate used was changed to 6.3 g and the supported amount of silver was 5 mass% based on the carrier.
  • the catalyst 5 was obtained in the same manner as the catalyst 4 except that the copper sulfate pentahydrate used was changed to 26.8 g and the supported amount of copper was changed to 10% by mass based on the carrier.
  • the catalyst 6 was obtained in the same manner as the catalyst 4 except that the copper sulfate pentahydrate used was changed to 13.2 g and the supported amount of copper was changed to 5% by mass based on the carrier.
  • the catalyst 8 was obtained in the same manner as the catalyst 7 except that the silver nitrate used was changed to 12.7 g and the supported amount of silver was 10% by mass based on the carrier.
  • the catalyst 9 was obtained in the same manner as the catalyst 7 except that the silver nitrate used was changed to 6.3 g and the supported amount of silver was 5% by mass based on the carrier.
  • Example 1 In a fixed bed flow type reaction tube, catalyst 1, catalyst 2 and catalyst 3 were filled in this order with 8 ml, 8 ml and 8 ml, respectively, to prepare a catalyst layer in which the above three kinds of zeolite were laminated.
  • fuel 1 (city gas) having the composition shown in Table 1 is circulated under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure. It was.
  • Example 2 Desulfurization was performed in the same manner as in Example 1 except that fuel 2 (city gas) having the composition shown in Table 1 was circulated under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure instead of fuel 1. Went. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Example 3 Desulfurization was performed in the same manner as in Example 1 except that fuel 3 (city gas) having the composition shown in Table 1 was circulated under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure instead of fuel 1. Went. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Example 4 A fixed bed flow type reaction tube was filled with catalyst 4, catalyst 5 and catalyst 6 in this order at 8 ml, 8 ml and 8 ml, respectively, to prepare a catalyst layer in which the above three types of zeolite were laminated.
  • fuel 2 (city gas) having the composition shown in Table 1 is circulated under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure. It was. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Example 5 In a fixed bed flow type reaction tube, catalyst 7, catalyst 8 and catalyst 9 were filled in this order at 8 ml, 8 ml and 8 ml, respectively, to prepare a catalyst layer in which the above three kinds of zeolite were laminated.
  • fuel 2 (city gas) having the composition shown in Table 1 is circulated under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure. It was. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Example 1 A fixed bed flow type reaction tube was filled with the catalyst 2 at a filling amount of 24 ml to prepare a catalyst layer.
  • Fuel 1 (city gas) having the composition shown in Table 1 was circulated through this reaction tube under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Comparative Example 2 Desulfurization was performed in the same manner as in Comparative Example 1 except that fuel 2 (city gas) having the composition shown in Table 1 was circulated under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure instead of fuel 1. Went. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Example 4 A fixed bed flow-type reaction tube was filled with the catalyst 5 at a filling amount of 24 ml to prepare a catalyst layer.
  • a fuel 2 (city gas) having the composition shown in Table 1 was circulated through this reaction tube under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • Example 5 A fixed bed flow type reaction tube was filled with the catalyst 8 at a filling amount of 24 ml to prepare a catalyst layer.
  • a fuel 2 (city gas) having the composition shown in Table 1 was circulated through this reaction tube under the conditions of GHSV: 6000 h ⁇ 1 , temperature of 30 ° C., and atmospheric pressure. Then, the sulfur breakthrough time was measured in the same manner as in Example 1.
  • a plurality of zeolites having different active metal concentrations are arranged in order from the highest to the lowest active metal concentration from the upstream side to the downstream side in the distribution direction of the city gas that is a hydrocarbon fuel.
  • a highly durable fuel cell desulfurization system capable of maintaining a desired desulfurization performance for a longer period of time even when a hydrocarbon-based fuel containing a desulfurization agent poison is supplied, hydrogen A manufacturing system, a fuel cell system, and a hydrocarbon-based fuel desulfurization method can be provided.

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Abstract

L'invention concerne un système de désulfuration pour pile à combustible comprenant une unité de désulfuration pour éliminer les composés du soufre d'un hydrocarbure en circulation qui contient des composés du soufre. L'unité de désulfuration est constituée d'un métal actif supportant une pluralité de zéolites en différentes concentrations et comprend un agent de désulfuration, la pluralité de zéolites étant disposée entre le côté amont du sens de circulation de l'hydrocarbure et le côté aval, dans l'ordre de la plus forte concentration de métal actif vers la plus faible.
PCT/JP2011/079719 2010-12-28 2011-12-21 Système de désulfuration pour pile à combustible, système de production d'hydrogène pour pile à combustible, système à pile à combustible et procédé de désulfuration pour hydrocarbure WO2012090837A1 (fr)

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JP2003020489A (ja) * 2001-07-05 2003-01-24 Tokyo Gas Co Ltd 燃料ガスの脱硫装置及び脱硫方法
WO2004058927A1 (fr) * 2002-12-26 2004-07-15 Idemitsu Kosan Co., Ltd. Procede permettant d'oter un compose de soufre dans un gaz contenant un hydrocarbure
JP2006137649A (ja) * 2004-11-15 2006-06-01 Nippon Oil Corp 水素製造装置および燃料電池システムの起動停止方法
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