WO2013146198A1 - Système de désulfuration, système de fabrication d'hydrogène, système de pile à combustible, procédé de désulfuration de combustible et procédé de fabrication d'hydrogène - Google Patents

Système de désulfuration, système de fabrication d'hydrogène, système de pile à combustible, procédé de désulfuration de combustible et procédé de fabrication d'hydrogène Download PDF

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WO2013146198A1
WO2013146198A1 PCT/JP2013/056498 JP2013056498W WO2013146198A1 WO 2013146198 A1 WO2013146198 A1 WO 2013146198A1 JP 2013056498 W JP2013056498 W JP 2013056498W WO 2013146198 A1 WO2013146198 A1 WO 2013146198A1
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desulfurization
fuel
hydrogen
catalyst
volume
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Japanese (ja)
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貴美香 石月
圭行 永易
一則 宮沢
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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
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    • 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
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/755—Nickel
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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
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    • 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
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    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • 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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    • 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
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    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
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    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/066—Integration with other chemical processes with fuel cells
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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
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
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    • 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
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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 desulfurization system, a hydrogen production system, a fuel cell system, a fuel desulfurization method, and a hydrogen production method.
  • a gas containing hydrogen as a main component is used, and natural gas, LPG, city gas, naphtha, kerosene and other hydrocarbons are used as the raw material.
  • the raw material containing the hydrocarbon contains a sulfur compound as an impurity or additive.
  • a sulfur compound as an impurity or additive.
  • noble metal, copper, or the like is used in a reduced state as a catalyst used for reforming raw materials until fuel hydrogen for fuel cells is produced, and further for a cathode electrode.
  • 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. Therefore, desulfurization of the raw material is usually performed using a metal-supported zeolite or the like (for example, see Patent Document 1 below).
  • the expansion of fuel used is required for the spread of fuel cells.
  • the use of biomass-derived fuel is expected from the viewpoint of resource constraints and environmental considerations.
  • the utilization of biogas containing oxygen gas or the like for the purpose of carbon neutral has been attempted for a part of city gas used for hot water supply, cooking, heating and the like.
  • the desulfurization system according to the present invention is a fuel that supplies a fuel composition containing a hydrocarbon fuel, a sulfur compound, 1 volume ppm to 4 volume% oxygen, and 1 volume% to 50 volume% hydrogen to the subsequent stage.
  • hydrogen is added to a raw fuel containing oxygen and a sulfur compound, and the desulfurization part is desulfurized at a specific desulfurization catalyst and a specific desulfurization temperature, so that the raw fuel containing oxygen is obtained. Sufficient desulfurization performance can be obtained.
  • the desulfurization catalyst may further contain one or more metals selected from the group consisting of Zn, Cu, Fe and Co.
  • hydrogen sulfide is sometimes generated from a sulfur compound in order to contain hydrogen in the raw fuel, but the desulfurization catalyst is one or more selected from the group consisting of Zn, Cu, Fe and Co.
  • the desulfurization catalyst is one or more selected from the group consisting of Zn, Cu, Fe and Co.
  • the desulfurization section includes the desulfurization catalyst (sometimes referred to as “first desulfurization catalyst”) and Zn, Cu, Fe, and Co provided in the subsequent stage of the desulfurization catalyst. And a second desulfurization catalyst containing one or more metals selected from the group.
  • first desulfurization catalyst sometimes referred to as “first desulfurization catalyst”
  • second desulfurization catalyst containing one or more metals selected from the group.
  • hydrogen sulfide may be generated as described above, but the desulfurization part is composed of the desulfurization catalyst and the group consisting of Zn, Cu, Fe, and Co provided in the subsequent stage of the desulfurization catalyst. If the second desulfurization catalyst containing one or more selected metals is included, hydrogen sulfide can be sufficiently removed by the second desulfurization catalyst.
  • a hydrogen production system includes the desulfurization system according to the present invention and a hydrogen generation unit that generates hydrogen from the fuel composition desulfurized in the desulfurization unit.
  • the desulfurization system according to the present invention by providing the desulfurization system according to the present invention, it is possible to suppress the sulfur compound from flowing into the hydrogen generation section over a long period of time, thereby improving the production efficiency of hydrogen over a long period. It is possible to maintain sufficient over the entire range.
  • a fuel cell system according to the present invention includes the above-described hydrogen production system of the present invention. According to the fuel cell system of the present invention, the power generation efficiency can be sufficiently maintained over a long period of time by including the hydrogen production system of the present invention.
  • the fuel desulfurization method according to the present invention comprises a fuel composition containing a hydrocarbon fuel, a sulfur compound, 1 volume ppm to 4 volume% oxygen, and 1 volume% to 50 volume% hydrogen, and Ni. And a step of desulfurization at 150 to 450 ° C. using the desulfurization catalyst contained.
  • hydrogen is added to the raw fuel, and desulfurization is performed at a specific desulfurization catalyst and a specific desulfurization temperature, thereby obtaining sufficient desulfurization performance for the raw fuel containing oxygen. be able to.
  • the hydrogen production method according to the present invention includes a step of reforming the hydrocarbon fuel desulfurized by the fuel desulfurization method according to the present invention to obtain hydrogen.
  • a desulfurization system capable of obtaining a sufficient desulfurization performance while applying a raw fuel containing oxygen, a hydrogen production system and a fuel cell system using the same are provided.
  • the present invention also provides a fuel desulfurization method that can sufficiently desulfurize oxygen-containing raw fuel and a hydrogen production method using the same.
  • 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, and each part is connected by piping in the flow shown in FIG. 1.
  • the fuel supply unit 2 constitutes a desulfurization system 20 together with the desulfurization unit 3, and supplies the fuel composition to the desulfurization unit 3.
  • the fuel composition contains a hydrocarbon fuel, a sulfur compound, 1 volume ppm to 4 volume% oxygen, and 1 volume% to 50 volume% hydrogen.
  • the oxygen content in the fuel composition is preferably 2% by volume or less, and more preferably 0.5% by volume or less. Further, in the present embodiment, since sufficient desulfurization performance can be obtained for the raw fuel containing oxygen, the oxygen content in the fuel composition may be 0.1% by volume or more, It may be 0.2% by volume or more.
  • the hydrogen content in the fuel composition is preferably 1% to 50% by volume, more preferably 5% to 40% by volume, and still more preferably 10% to 35% by volume.
  • the fuel composition can be prepared, for example, by adding a gas containing hydrogen to a raw fuel containing a hydrocarbon fuel, a sulfur compound, and oxygen.
  • the hydrogen source added to the hydrocarbon-based fuel is not particularly limited, but, for example, a part of hydrogen generated in the hydrogen generation unit 4 described later can be used (not shown).
  • hydrocarbon fuel a compound containing carbon atoms and hydrogen atoms in the molecule (may contain other elements such as oxygen) or a mixture thereof can be used.
  • hydrocarbon fuels include hydrocarbons, alcohols, ethers, and biofuels. These hydrocarbon fuels include those derived from conventional fossil fuels such as petroleum and coal, synthesis gas, and the like. Those derived from synthetic fuels and those derived from biomass can be used as appropriate.
  • hydrocarbons examples include hydrocarbon compounds such as methane, ethane, propane, and butane, natural gas, LPG (liquefied petroleum gas), city gas, town gas, gasoline, naphtha, kerosene, and light oil.
  • alcohols examples include methanol and ethanol.
  • ethers examples include dimethyl ether.
  • biofuel examples include biogas, bioethanol, biodiesel, and biojet.
  • the hydrocarbon fuel may contain alcohols such as methanol and ethanol, and ethers such as dimethyl ether.
  • a gas containing methane as a main component for example, city gas, town gas, natural gas, biogas, etc.
  • LPG supplied through a pipeline
  • the hydrocarbon fuel containing biogas generally contains oxygen.
  • the oxygen content in the hydrocarbon fuel is usually 1 ppm to 4% by volume, although it depends on the degree of use of biogas and the like.
  • the oxygen content is JIS K2301 “Fuel gas and natural gas—analysis / test method—general component analysis method (gas chromatographic method)” or JIS K0225 “trace component test method in dilution gas and zero gas”. It can measure according to.
  • the hydrocarbon fuel preferably 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.
  • Hydrocarbon fuels generally contain sulfur compounds.
  • the sulfur compound include a sulfur compound originally mixed in hydrocarbons and the like and a compound contained in an odorant for detecting gas leakage.
  • the sulfur compound originally mixed in hydrocarbons include hydrogen sulfide (H 2 S), carbonyl sulfide (COS), carbon disulfide (CS 2), and the like.
  • odorants include alkyl sulfides, mercaptans, and the like. More specifically, diethyl sulfide (DES), dimethyl sulfide (DMS), ethyl methyl sulfide (EMS), tetrahydrothiophene (THT), tert-butyl mercaptan.
  • TBM isopropyl mercaptan
  • DMDS dimethyl disulfide
  • DEDS diethyl disulfide
  • the sulfur compound content is usually about 0.1 to 10 ppm by mass in terms of sulfur atom based on the total amount of hydrocarbon fuel.
  • components other than those described above may be included in a range that does not adversely affect the characteristics of the fuel cell system.
  • the fuel composition supplied from the fuel supply unit 2 is desulfurized in the desulfurization unit 3.
  • the sulfur compound contained in the fuel composition is removed by the desulfurization catalyst in the desulfurization unit 3 in order to poison the reforming catalyst in the hydrogen generation unit 4 and the electrode catalyst in the cell stack 5.
  • a desulfurization catalyst containing Ni is heated to 150 to 400 ° C. and used.
  • the desulfurization catalyst further contains one or more metals selected from the group consisting of Zn, Cu, Fe and Co (hereinafter sometimes collectively referred to as “second supported metal”). Also good. Moreover, elements such as Mo and P may be added to the desulfurization catalyst.
  • the desulfurization catalyst can also be referred to as a catalyst containing a carrier and Ni supported on the carrier.
  • the carrier include silica, alumina, titania, zirconia, etc. Among these, silica or alumina is preferable.
  • the Ni loading method include an impregnation method, a deposition method, a coprecipitation method, a kneading method, an ion exchange method, and a pore filling method, and among these, the coprecipitation method is particularly suitable.
  • the content of Ni in the desulfurization catalyst is preferably 10 to 70% by mass and more preferably 20 to 60% by mass based on the total amount of the desulfurization catalyst in terms of oxide.
  • the content of Ni is in the above range, desulfurization performance is further improved and higher catalyst strength is obtained.
  • the content of the second supported metal is preferably 0 to 40% by mass, more preferably 0 to 15% by mass in terms of oxide, based on the total amount of the desulfurization catalyst.
  • Ni starting material for producing the desulfurization catalyst varies depending on the loading method and can be appropriately selected. Specific examples of Ni starting materials include nickel chloride, nickel nitrate, nickel carbonate and hydrates thereof.
  • the starting material for the second supported metal in producing the desulfurization catalyst varies depending on the loading method and can be appropriately selected.
  • Specific examples of the starting material for the second supported metal include chlorides of the second supported metal, nitrates of the second supported metal, and hydrates thereof.
  • an aqueous solution containing a Ni starting material (and optionally a second supported metal starting material) and an aqueous solution containing a carrier (for example, silica sol) and a base are mixed to precipitate.
  • Ni can be supported on the support by drying and baking the resulting precipitate.
  • the firing is usually performed in an air or nitrogen atmosphere, and the firing temperature can be, for example, 200 to 800 ° C.
  • a suitable desulfurization catalyst can be obtained by performing a reduction treatment.
  • the desulfurization catalyst is preferably a catalyst obtained by reducing a catalyst precursor containing a carrier and Ni oxide supported on the carrier.
  • the catalyst precursor may further contain an oxide of the second supported metal.
  • the Ni content in the catalyst precursor is preferably 10 to 70% by mass and more preferably 20 to 60% by mass in terms of oxide, based on the total amount of the catalyst precursor.
  • the content of the second supported metal in the catalyst precursor is preferably 0 to 40% by mass, more preferably 0 to 15% by mass in terms of oxide, based on the total amount of the catalyst precursor.
  • the reduction treatment can be performed, for example, by heating to 200 to 500 ° C. in a reducing atmosphere (for example, in a hydrogen stream).
  • the desulfurization unit 3 may be filled with a desulfurization catalyst that has been previously reduced, or the catalyst precursor may be filled in the desulfurization unit 3 and the catalyst precursor may be reduced in the desulfurization unit 3. it can.
  • the desulfurization unit 3 includes the desulfurization catalyst, and a second desulfurization catalyst containing one or more metals selected from the group consisting of Zn, Cu, Fe, and Co, which is provided in the subsequent stage of the desulfurization catalyst. You may have.
  • the second desulfurization catalyst include ZnO, activated carbon, and zeolite. Of these, ZnO is preferable.
  • hydrogen sulfide may be generated from a sulfur compound in order to contain hydrogen in the raw fuel.
  • the desulfurization catalyst has a second supported metal or the desulfurization section has a second desulfurization catalyst. By doing so, hydrogen sulfide is sufficiently removed in the desulfurization section 3.
  • the fuel composition is desulfurized by bringing the fuel composition into contact with the desulfurization catalyst.
  • the temperature during desulfurization is 150 to 450 ° C., preferably 150 to 400 ° C., more preferably 200 to 350 ° C.
  • GHSV is 10 to 20000 h ⁇ 1 , preferably 10 to 7000 h ⁇ 1 . It is preferable to select between.
  • GHSV is lower than 10 h ⁇ 1 , desulfurization performance is improved, but since a large amount of desulfurization catalyst is used, it is necessary to use an excessive desulfurizer as the desulfurization section 3.
  • liquid fuel can also be used as the hydrocarbon fuel, and in that case, it is preferable to select LHSV between 0.01 and 100 h ⁇ 1 .
  • the working pressure 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, and more preferably normal pressure to 0.2 MPa. Most preferably, it can be implemented.
  • the fuel composition from which the sulfur compound 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 generation unit 4 is configured to remove carbon monoxide in the hydrogen-rich gas. (For example, a shift reaction part and a selective oxidation reaction part).
  • the hydrogen generation unit 4 supplies a hydrogen rich gas to the anode 12 of the cell stack 5.
  • the reforming catalyst is not particularly limited, and a general reforming catalyst can be used.
  • a reforming catalyst in which a porous inorganic oxide selected from alumina, silica and the like is loaded with a metal selected from Group VIII metals such as nickel, cobalt, iron, ruthenium, rhodium, iridium, platinum, etc. be able to.
  • the reforming catalyst include a catalyst carrier containing cerium oxide or a rare earth element oxide mainly composed of cerium oxide and an active metal supported on the carrier.
  • the reforming catalyst preferably uses Ru or Rh as the active metal.
  • 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 above 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.
  • the cerium oxide is not particularly limited, but second 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 (CeOH 3 , CeOH 4 .H 2 O, etc.), cerium carbonate (Ce 2 (CO 3 ) 3 .8 H 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.
  • Aluminum oxide includes alumina and double oxides of aluminum and other elements such as silicon, copper, iron, and titanium. Typical examples of double oxides include silica alumina.
  • alumina is particularly desirable, and the alumina is not particularly limited, and any crystal form such as ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , etc. can be used. Is preferred.
  • 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.
  • the aluminum oxide used in the present invention 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 containing cerium oxide as a main component in the catalyst carrier used in the present invention is 5 to 40% by mass, 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.
  • composition ratio of the aluminum oxide in the catalyst carrier of the reforming catalyst is 60 to 95% by mass, preferably 65 to 90% by mass.
  • 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.
  • water vapor is supplied from the water vaporization unit 8 in order to reform the hydrocarbon fuel.
  • 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 (not shown) 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 specific desulfurization catalyst is used, the desulfurization temperature is set to a specific range, and the oxygen content of the raw fuel is 1 ppm by volume or more.
  • the fuel desulfurization method according to the present embodiment includes a fuel composition containing a hydrocarbon fuel, a sulfur compound, 1 volume ppm to 4 volume% oxygen, and 1 volume% to 50 volume% hydrogen. And a step of desulfurizing at 150 to 450 ° C. using a desulfurization catalyst containing
  • examples of the fuel composition include the fuel compositions described above.
  • Specific means for bringing the fuel composition into contact with the desulfurization catalyst includes the fuel supply unit 2 and the desulfurization unit 3 described above. That is, this method can be implemented by supplying the fuel composition to the desulfurization unit 3 by the fuel supply unit 2 and bringing the supplied fuel composition into contact with the desulfurization catalyst in the desulfurization unit 3.
  • the desulfurization conditions are usually conditions in which the fuel is vaporized.
  • the desulfurization temperature is 150 to 450 ° C, preferably 150 to 400 ° C, more preferably 200 to 350 ° C.
  • GHSV is 10 to 20000 h ⁇ 1 , preferably 10 to 7000 h ⁇ 1 . It is preferable to select between.
  • GHSV is lower than 10 h ⁇ 1 , desulfurization performance is improved, but a large amount of desulfurization agent is used, so that it is necessary to use an excessive desulfurizer.
  • the desulfurization performance is further improved by setting the GHSV to 20000 h ⁇ 1 or less.
  • liquid fuel can also be used as the hydrocarbon fuel, and in that case, it is preferable to select LHSV between 0.01 and 100 h ⁇ 1 .
  • the working pressure 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, and more preferably normal pressure to 0.2 MPa. Most preferably, it can be implemented.
  • the method for producing hydrogen according to the present embodiment reforms the hydrocarbon fuel in the fuel composition desulfurized by the desulfurization method to generate hydrogen (hydrogen rich gas).
  • the reforming method is not particularly limited as described above, 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 reforming catalyst preferably uses Ru or Rh as the active metal, and the catalyst carrier is cerium oxide or 5 to 40% by mass of a rare earth element oxide mainly composed of cerium oxide, aluminum oxide.
  • a carrier containing 60 to 95% by mass is preferable.
  • steam is supplied from the water vaporization unit 8 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.
  • catalyst precursor A On a commercially available ⁇ -alumina support, nickel nitrate hexahydrate having a metal Ni content of 8% by mass was supported by an impregnation method, dried at 120 ° C. for 3 hours, and then calcined at 400 ° C. for 3 hours to obtain Ni / Al 2. An O 3 catalyst (hereinafter referred to as catalyst precursor A) was obtained. The supported amount of nickel oxide in the catalyst precursor A was 10% by mass based on the total amount of the catalyst precursor A.
  • the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 100 g of baked powder.
  • the obtained calcined powder was extrusion molded at 1 mm ⁇ to obtain catalyst precursor B.
  • catalyst precursor C On a commercially available ⁇ -alumina support, copper nitrate trihydrate having a metal Cu content of 26 mass% was supported by an impregnation method, dried at 120 ° C. for 3 hours, and then calcined at 400 ° C. for 3 hours to obtain Cu / Al 2 An O 3 catalyst (hereinafter referred to as catalyst precursor C) was obtained.
  • the supported amount of copper oxide in the catalyst precursor C was 10% by mass based on the total amount of the catalyst precursor C.
  • Fuel gas containing dimethyl sulfide (DMS) 80 volume ppm and oxygen concentration 0.5 volume% 51 volume% methane, hydrogen 32 volume%, carbon monoxide 4 volume%, carbon dioxide 13 volume% (oxygen in the fuel gas) The concentration was 0.26 vol%) at GHSV 1000 h ⁇ 1 at normal pressure and 350 ° C.
  • the sulfur concentration at the outlet of the reaction tube was measured by SCD (Sulfur Chemiluminescence Detector) gas chromatography.
  • SCD sulfur Chemiluminescence Detector
  • Example 2 An experiment was performed in the same manner as in Example 1 except that the oxygen concentration of methane gas was changed to 4.0% by volume (the oxygen concentration in the fuel gas was 2.0% by volume), and desulfurization performance was obtained.
  • Example 3 Comparative Example 3
  • Example 3 An experiment was performed in the same manner as in Example 1 except that the hydrogen content of the fuel gas was changed to 8% by volume, 1% by volume, or 0.5% by volume, and desulfurization performance was obtained.
  • the desulfurization performance of Reference Example 1 was 0.98, the desulfurization performance of Reference Example 3 was 0.88, the desulfurization performance of Reference Example 4 was 0.80, and the desulfurization performance of Reference Example 4 was 1. .3.

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Abstract

L'invention concerne un système de désulfuration, qui comporte : une section d'alimentation de combustible pour adresser à un étage ultérieur une composition de combustible qui comprend un combustible à base d'hydrocarbure, un composé de soufre, 1 ppm en volume à 4 % en volume d'oxygène, et 1-50 % en volume d'hydrogène ; et une section de désulfuration pour désulfurer la composition de combustible adressée en provenance de la section d'alimentation de combustible à 150-450°C à l'aide d'un catalyseur de désulfuration contenant du Ni.
PCT/JP2013/056498 2012-03-28 2013-03-08 Système de désulfuration, système de fabrication d'hydrogène, système de pile à combustible, procédé de désulfuration de combustible et procédé de fabrication d'hydrogène WO2013146198A1 (fr)

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JPS61163568A (ja) * 1985-01-11 1986-07-24 Mitsubishi Heavy Ind Ltd 一体型脱硫装置
JPH04159393A (ja) * 1990-10-23 1992-06-02 Hitachi Ltd 高カロリー都市ガスの製造方法
JPH11214024A (ja) * 1998-01-26 1999-08-06 Mitsubishi Electric Corp りん酸型燃料電池発電設備

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JP4096128B2 (ja) * 1997-08-21 2008-06-04 大阪瓦斯株式会社 脱硫剤の製造方法および炭化水素の脱硫方法

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Publication number Priority date Publication date Assignee Title
JPS61163568A (ja) * 1985-01-11 1986-07-24 Mitsubishi Heavy Ind Ltd 一体型脱硫装置
JPH04159393A (ja) * 1990-10-23 1992-06-02 Hitachi Ltd 高カロリー都市ガスの製造方法
JPH11214024A (ja) * 1998-01-26 1999-08-06 Mitsubishi Electric Corp りん酸型燃料電池発電設備

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