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WO2008001632A1 - Catalyseur pour reformage à la vapeur, appareil de production d'hydrogène, et système de pile à combustible - Google Patents

Catalyseur pour reformage à la vapeur, appareil de production d'hydrogène, et système de pile à combustible Download PDF

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Publication number
WO2008001632A1
WO2008001632A1 PCT/JP2007/062190 JP2007062190W WO2008001632A1 WO 2008001632 A1 WO2008001632 A1 WO 2008001632A1 JP 2007062190 W JP2007062190 W JP 2007062190W WO 2008001632 A1 WO2008001632 A1 WO 2008001632A1
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Prior art keywords
catalyst
oxide
mass
earth element
steam reforming
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Ceased
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PCT/JP2007/062190
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English (en)
Japanese (ja)
Inventor
Yasushi Hashimoto
Yasushi Satoh
Takaya Matsumoto
Yukihiro Sugiura
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Eneos Corp
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Nippon Oil Corp
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Priority to KR1020097001546A priority Critical patent/KR101403733B1/ko
Priority to JP2008522440A priority patent/JP5072841B2/ja
Publication of WO2008001632A1 publication Critical patent/WO2008001632A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—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 characterised by the catalyst
    • 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
    • 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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • 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
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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 steam reforming catalyst, a hydrogen production apparatus using the steam reforming catalyst, and a fuel cell system having the hydrogen production apparatus.
  • hydrocarbon reforming technology for hydrocarbon compounds, which reacts hydrocarbon compounds with steam to obtain hydrogen, carbon monoxide, carbon dioxide, methane, etc. .
  • the steam reforming method is widely used because the equipment is cheaper than the partial oxidation method.
  • kerosene is preferred as the raw material hydrocarbon for fuel cells because of its energy density, economy, and ease of handling.
  • the nickel-based catalyst causes carbon deposition, the raw material hydrocarbon is limited to about naphtha from natural gas. It was done.
  • ⁇ -alumina was generally used as the catalyst carrier, but the mechanical strength was not so strong, so the catalyst was pulverized during DSS (Daily Start and Shutdown) operation of a fuel cell with a large heat load. Problems such as an increase in differential pressure have occurred.
  • alumina As a typical catalyst carrier having high mechanical strength, alumina can be mentioned. However, in conventional steam reforming catalysts using alumina, the raw material hydrocarbon is about naphtha and the effect of suppressing carbon deposition is insufficient. (See Patent Document 2).
  • Patent Document 1 Japanese Patent Laid-Open No. 4-3 6 3 1 40
  • Patent Document 2 Japanese Patent Laid-Open No. Hei 4 1590-48
  • the present invention provides a steam reforming catalyst having a low pressure, a low steam / carbon ratio, a low carbon deposition, a long life and a high mechanical strength, and a hydrogen production apparatus and a fuel cell using the catalyst. It also provides a system.
  • the present inventors can achieve both by using a specific steam reforming catalyst.
  • the present invention has been found and the present invention has been completed. That is, according to the present invention, 2 to 25 masses per ⁇ - alumina is added to spun alumina having a pore volume of 50 nm or more and a pore volume of 0.2 to 1.0 m 17 g. /. Rare earth element oxide and 0.5:! ⁇ 15 mass.
  • Steam reforming characterized in that a support obtained by supporting an oxide / alkaline earth element oxide of 0 / is supported with 0.3 to 5% by mass of ruthenium as an active metal based on the support. Relates to a catalyst.
  • the present invention uses the oxide for one or more rare earth elements selected from scandium, yttrium, lanthanum and cerium as the rare earth element oxide. Relates to the catalyst.
  • the present invention also provides the water vapor as described above, wherein the alkali earth element oxide is an oxide of one or more alkaline earth elements selected from magnesium, calcium, strontium and barium.
  • the present invention relates to a reforming catalyst.
  • the present invention also relates to the steam reforming catalyst as described above, wherein the ⁇ -alumina has a specific surface area of 3 to 30 m 2 / g.
  • the present invention also relates to a hydrogen production apparatus characterized in that a reformed gas containing hydrogen as a main component is obtained from a hydrocarbon compound by a steam reforming reaction using the steam reforming catalyst described above.
  • the present invention also relates to a fuel cell system comprising the hydrogen production apparatus described above. [The invention's effect]
  • the steam reforming catalyst of the present invention has a specific amount of ruthenium as an active metal supported on a carrier obtained by supporting specific amounts of rare earth element oxides and alkaline earth element oxides on specific ⁇ alumina. It consists of
  • the catalyst carrier component spun alumina with macropores with a pore diameter of 50 nm or more is used.
  • the pore volume with a pore diameter of 50 nm or more needs to be 0.2 to 1. Oml / g.
  • the pore volume is smaller than 0.2 m 1 Zg, the catalytic activity becomes insufficient, which is not preferable.
  • the pore volume is larger than 1.
  • Oml / g the catalyst strength is insufficient, which is not preferable.
  • the BET specific surface area of ⁇ -alumina is preferably 3 to 30 m 2 / g.
  • the BET specific surface area is smaller than 3 m 2 / g, the catalytic activity is insufficient, which is not preferable.
  • the BET specific surface area is larger than 30 in 2 / g, the catalyst strength is insufficient, which is not preferable.
  • rare earth element it is preferable to use one or more rare earth elements selected from scandium, yttrium, lanthanum and cerium, and lanthanum opium cerium is more preferable.
  • the content of rare earth elements in the catalyst carrier, as a rare earth oxide, with respect to alpha alumina, outside rate is required to be 2 to 25 mass 0/0, Preferably 5-20 mass. / 0 , more preferably 10 to 15 mass. / 0 .
  • the content of the rare earth element oxide is more than 25% by mass, aggregation is increased and the ratio of the metal that appears on the surface is extremely decreased.
  • the content is less than 2% by mass, carbon deposition of the rare earth element is not preferable. The suppression effect is insufficient and is not preferable.
  • Alkaline earth elements include magnesium, calcium, strontium and It is preferable to use one or more kinds of alkaline earth metals selected from piperium, and magnesium and strontium are more preferable.
  • the content of alkaline earth element in the catalyst carrier is 0.1 to 15 mass in terms of the external ratio (alpha alumina weight basis) with respect to alpha alumina as the alkaline earth element oxide. % and it is necessary, preferably 0.5 to 1 2 weight 0/0, more preferably 1 to 1 0% by weight.
  • the content of alkaline earth element oxide is more than 15% by mass, aggregation is increased and the proportion of active metal that appears on the surface is extremely decreased.
  • the content is less than 0.1% by mass This is not preferable because the effect of suppressing the precipitation of carbon by alkaline earth elements and the effect of improving the activity are insufficient.
  • the content of ruthenium in the catalyst of the present invention is such that the ruthenium atom is an external ratio (based on the weight of the support) with respect to the support obtained by supporting the rare earth element oxide and the alkaline earth element oxide on ⁇ -alumina. 0. it is necessary that a 3 to 5 mass 0/0, preferably from 1 to 4 wt%, more preferably 2 to 3 wt%.
  • the content of ruthenium is more than 5% by mass, the active metal agglomerates and the proportion of the metal coming out on the surface is extremely reduced.
  • the content is less than 0.3% by mass, sufficient activity is obtained. As a result, it is necessary to use a large amount of supported catalyst, which causes problems such as the need to enlarge the reactor more than necessary.
  • the catalyst strength of the steam reforming catalyst of the present invention is preferably such that the catalyst crushing strength by the Kiya measurement method is 50 kg or more per catalyst particle. If the catalyst crushing strength is less than 5 ON, the catalyst is cracked and pulverized during the operation of the fuel cell, which is not preferable.
  • the method of supporting the rare earth element and the alkaline earth element on the ⁇ -alumina there is no particular limitation on the method of supporting the rare earth element and the alkaline earth element on the ⁇ -alumina, and a known method such as a normal impregnation method or a pore fill method can be employed. Usually, it is dissolved in a solvent such as water, ethanol, or acetone as a metal salt or complex, and impregnated on a carrier.
  • a solvent such as water, ethanol, or acetone
  • the metal salt or metal complex to be supported chloride, nitrate, sulfate, acetate, acetoacetate and the like are preferably used.
  • the loading process there is no particular limitation on the loading process, and the impregnation can be performed simultaneously or sequentially.
  • the carrier carrying rare earth elements and alkaline earth elements is 3 5 0 Baking is preferably performed at a temperature of ⁇ 100 ° C. When the temperature is lower than 35 ° C., immobilization of the support element on the carrier is not preferable. On the other hand, when the temperature is higher than 100 ° C., the supported elements are aggregated, which is not preferable.
  • the firing atmosphere is preferably under air, and the gas flow rate is not particularly limited. The firing time is preferably 2 hours or more. When the time is shorter than 2 hours, immobilization of the supported element on the carrier is not preferable.
  • ruthenium is then supported.
  • a known method such as a normal impregnation method or a pore fill method can be employed. Usually, it is dissolved in a solvent such as water, ethanol, or acetone as a metal salt or complex, and impregnated on a carrier.
  • a solvent such as water, ethanol, or acetone
  • the metal salt or metal complex to be supported chloride, nitrate, sulfate, acetate, acetoacetate and the like are preferably used.
  • the impregnation can be performed once or several times.
  • moisture is removed by drying.
  • a temperature of 100 to 150 ° C. under air or inert gas is preferably used.
  • the supported catalyst thus obtained is activated by performing reduction treatment or metal immobilization treatment as necessary.
  • the treatment method is not particularly limited, and gas phase reduction or liquid phase reduction under hydrogen flow is preferably used.
  • the form of the catalyst for steam reforming of this invention there is no restriction
  • a catalyst that is formed into a tablet and sized to an appropriate range after pulverization a catalyst that is extruded by adding an appropriate binder, and a powdered catalyst.
  • a metal is applied to a carrier that has been molded into tablets and sized to an appropriate range after pulverization, a carrier that has been extruded, a powder or a carrier that has been molded into a suitable shape such as a sphere, ring, tablet, cylinder, or flake.
  • a supported catalyst can be used, but a spherical catalyst is preferred from the viewpoint of mechanical strength.
  • a catalyst in which the catalyst itself is formed into a monolith shape, a Hucam shape, or the like, or a monolith using a suitable material and a catalyst coated on a honeycomb or the like can be used.
  • a flow type fixed bed reactor is preferably used as a form of the reactor used for the steam reforming reaction.
  • the shape of the reactor is not particularly limited, and can be any known shape depending on the purpose of each process, such as a cylindrical shape or a flat plate shape. It is also possible to use a fluidized bed reactor.
  • the steam reforming reaction in the present invention refers to a reaction in which hydrocarbon compounds are reacted with steam in the presence of a catalyst to convert to a reforming gas containing carbon monoxide and hydrogen. When reacting with steam, it also includes the case of accompanying an oxygen-containing gas (autothermal reforming reaction).
  • the hydrocarbon compounds used as a raw material are organic compounds having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Specific examples include saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, etc. In addition, saturated aliphatic hydrocarbons and unsaturated aliphatic hydrocarbons are chain-like or cyclic. Can be used regardless. Aromatic hydrocarbons can be used regardless of whether they are monocyclic or polycyclic. Such hydrocarbon compounds can contain substituents. As the substituent, either a chain or a ring can be used, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, and an aralkyl group.
  • hydrocarbon compounds are substituted with a substituent containing a hetero atom such as a hydroxyl group, an aralkoxy group, a hydroxy carboel group, an aralkoxy carboxy group, or a formyl group. Also good.
  • Saturated aliphatic hydrocarbons such as octadecane, nonadecane and eicosane, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, pentene and hexene, cyclic hydrocarbons such as cyclopentane and cyclohexane, benzene, toluene and xyle And aromatic hydrocarbons such as naphthalene.
  • these mixtures can also be used conveniently.
  • natural gas, LPG, naphtha, gasoline, kerosene, light oil, and other materials that can be obtained industrially at low cost can be mentioned.
  • hydrocarbon compounds having a substituent containing a hetero atom include methanol, ethanol and pronox.
  • Nonole, butanol and dimethinoreethenole, phenol, fasol, acetate aldehyde, acetic acid and the like can be mentioned.
  • raw materials containing hydrogen, water, carbon dioxide, carbon monoxide, etc. can be used.
  • the residual hydrogen used in the reaction can be used as it is without being separated.
  • the concentration contained in the hydrocarbon compound used as a raw material is preferably 50 mass ppb or less, more preferably 20 mass ppb or less, and even more preferably 10 mass ppb as the mass of sulfur atoms. It is as follows. For this reason, if necessary, the raw material can be desulfurized in advance.
  • sulfur concentration in the raw material used in the desulfurization step there is no particular limitation on the sulfur concentration in the raw material used in the desulfurization step, and any material can be used as long as it can be converted to the sulfur concentration in the desulfurization step.
  • the desulfurization method an example is a method in which hydrodesulfurization is performed in the presence of an appropriate catalyst and hydrogen, and the generated hydrogen sulfide is absorbed by zinc oxide or the like.
  • the catalyst that can be used in this case include a catalyst containing, for example, Eckel-Molybden and copparto molybdenum.
  • a method of sorbing sulfur in the presence of an appropriate sorbent and, if necessary, coexisting with hydrogen can also be employed.
  • sorbents that can be used in this case include those composed mainly of copper and zinc as disclosed in Japanese Patent Nos. 2 6 5 4 5 15 and 2 6 8 8 7 4 9. Examples thereof include a sorbent and a sorbent mainly composed of nickel and zinc.
  • the method of performing the desulfurization step may be performed by a desulfurization process installed immediately before the steam reforming reactor, or a hydrocarbon treated in an independent desulfurization process may be used. .
  • the amount of steam introduced into the reaction system is defined as the ratio of the number of moles of water molecules to the number of moles of carbon atoms contained in the raw material hydrocarbon compounds (steam / carbon ratio).
  • the desired value is preferably in the range of 0.3 to 10, more preferably 0.5 to 5, and even more preferably 2 to 3. If this value is less than 0.3, coke is likely to deposit on the catalyst, and the hydrogen fraction cannot be increased. On the other hand, if it is greater than 10, the reforming reaction proceeds but the steam generating equipment There is a risk of enlarging steam recovery equipment. There are no particular restrictions on the method of addition, but it may be introduced into the reaction zone at the same time as the raw material hydrocarbon compounds, or may be introduced in portions from separate positions in the reactor zone or in several portions. Also good.
  • the space velocity of the flow material introduced into the reactor is GHSV, preferably 10 to 10, OOO h- Is 50 to 5, OOO h- more preferably 100-3, area by der of 000 h one 1.
  • LHSV is preferably in the range of 0.05 to 5.0 h ⁇ , more preferably 0.1 to 2.0 h ⁇ , and even more preferably 0.2 to 1. Oh.
  • the reaction temperature is not particularly limited, but is preferably in the range of 200 to 1,000 ° C, more preferably 300 to 900 ° C, and still more preferably 400 to 800 ° C.
  • the reaction pressure is also not particularly limited, and it is preferably carried out in the range of atmospheric pressure to 20 MPa, more preferably atmospheric pressure to 5 MPa, and further preferably atmospheric pressure to 1 MPa. If there is, it is also possible to carry out under atmospheric pressure.
  • the mixed gas containing carbon monoxide and hydrogen obtained by the steam reforming reaction using the catalyst of the present invention can be used as a fuel for a fuel cell as it is in the case of a solid oxide fuel cell.
  • carbon monoxide needs to be removed, such as phosphoric acid fuel cells and polymer electrolyte fuel cells, it is suitable for use as a raw material for fuel cell hydrogen by using a carbon monoxide removal process. be able to.
  • the present invention is also characterized in that a reformed gas containing hydrogen as a main component is obtained from a hydrocarbon (fuel) such as natural gas, LPG, naphtha, or kerosene by a steam reforming reaction using the catalyst. Providing manufacturing equipment. Furthermore, the present invention provides a fuel cell system having the hydrogen production apparatus. Hereinafter, the battery system of the present invention will be described.
  • FIG. 1 is a schematic view showing an example of the fuel cell system of the present invention.
  • the fuel in the fuel tank 3 flows into the desulfurizer 5 through the fuel pump 4.
  • the desulfurizer can be filled with, for example, a copper-zinc-based or nickel-zinc-based sorbent.
  • the hydrogen-containing gas from the carbon monoxide selective oxidation reactor 11 can be added.
  • the fuel desulfurized in the desulfurizer 5 is mixed with water from the water tank 1 through the water pump 2, introduced into the vaporizer 6, vaporized, and sent to the reformer 7.
  • the catalyst of the present invention is used as the catalyst for the reformer 7 and is filled in the reformer.
  • the reformer reaction tube is heated by a burner 1 8 using fuel anode offgas from the fuel tank as a fuel, preferably 200 to 1000 ° C, more preferably 300 to 90
  • the temperature is adjusted to 0 ° C, more preferably in the range of 400 to 800 ° C.
  • the reformed gas containing hydrogen and carbon monoxide produced in this way is passed through the high-temperature shift reactor 9, the low-temperature shift reactor 10, and the carbon monoxide selective oxidation reactor 11 in order, and is thus oxidized.
  • the carbon concentration is reduced to such an extent that it does not affect the characteristics of the fuel cell.
  • catalysts used in these reactors include iron-chromium catalysts for high-temperature shift reactor 9, copper-zinc-based catalysts for low-temperature shift reactor 10, and carbon monoxide selective oxidation reactor 1 1.
  • Can include ruthenium-based catalysts.
  • a catalyst carrier A is made of polyalumina having a pore volume of 0.4 ml / g and a surface area of 5 m 2 Zg.
  • catalyst carrier A is impregnated with cerium nitrate and magnesium nitrate so that the supported cerium oxide amount is 13% by mass and the supported magnesium oxide amount is 5% by weight. After drying at C for 8 hours or more, air calcination at 800 ° C for 8 hours. This is referred to as catalyst carrier B.
  • Example 3 magnesium nitrate is changed to calcium nitrate, and the amount of calcium oxide supported is 5% by mass as catalyst B.
  • Example 1 magnesium nitrate is changed to strontium nitrate, and the amount of supported strontium oxide is 5% by mass in terms of external ratio is defined as catalyst C.
  • Example 1 magnesium nitrate is changed to barium nitrate, and the amount of supported barium oxide is 5% by mass in terms of the external ratio is referred to as catalyst D.
  • Example 1 cerium nitrate was changed to scandium nitrate, and the amount of supported scandium oxide was 13 mass in external ratio. / 0 is the catalyst E.
  • Example 1 cerium nitrate is changed to yttrium nitrate, and the amount of supported yttrium oxide is 13% by mass in terms of the external ratio is defined as catalyst F.
  • Example 1 cerium nitrate is changed to lanthanum nitrate, and the amount of supported lanthanum oxide is 13% by mass in terms of external ratio is referred to as catalyst G. ,
  • the catalyst carrier A of Example 1 is used as catalyst H, which does not carry a rare earth element or an alkaline earth element and carries ruthenium directly in the same manner as in Example 1.
  • Example 1 the catalyst support A was replaced with ⁇ -alumina having a pore volume of 0.4 m 1 / g and a BET specific surface area of 170 m 2 / g as catalyst I.
  • Example 1 the amount of the supported cerium oxide is 1% by mass is designated as catalyst J.
  • Example 1 the amount of supported magnesium oxide was 0.08 mass. / 0 is defined as catalyst K. Steam reforming reaction>
  • the catalyst was evaluated by a steam reforming reaction.
  • For the reaction use a fixed-bed microreactor. W was used.
  • the catalyst loading is 50 cm 3 .
  • Desulfurized kerosene (density 0.793 gZc m 3 , sulfur content 0.05 mass! 11) was used as the hydrocarbon feedstock.
  • the reaction conditions are as follows. Inlet reaction temperature 500 ° C, Outlet reaction temperature 700 ° C, Reaction pressure 0.IMP a, Steam carbon ratio 3.0 mo 1 / mo 1, LHS V 1. 0 h _1 0
  • Table 1 shows the conversion rate of the raw materials obtained from the composition of the product gas after 1000 hours of reaction. Wherein the conversion of Table 1 is the percentage of the raw material was converted CO, the CH 4, C0 2, is obtained by calculating based on carbon.
  • the fuel cell system configured as shown in Fig. 1 was tested using kerosene as fuel and catalyst A. At this time, the steam / carbon ratio of the raw material gas introduced into the reformer 7 was set to 3.0. As a result of analyzing the gas at the anode inlet, it contained 72% by volume of hydrogen (excluding water vapor).
  • FIG. 1 is a schematic view showing an example of the fuel cell system of the present invention.

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Abstract

La présente invention concerne un catalyseur destiné à être utilisé dans le reformage à la vapeur, qui dépose seulement une faible quantité de carbone à basse pression et un faible rapport vapeur d'eau/carbone et possède une longue vie utile et une haute résistance mécanique. Le catalyseur comprend un support et du ruthénium (métal actif) supporté sur le support dans une quantité de 0,3 à 5 % en masse par rapport à la quantité du support. Le support est produit en supportant un oxyde d'un élément des terres rares et un oxyde d'un élément des terres rares alcalin sur de l'α-alumine qui possède un volume des pores de pores qui possèdent chacun une taille de pore de 50 nm ou plus de 0,2 à 1,0 ml/g, et l'oxyde d'un élément des terres rares et l'oxyde d'un élément des terres rares alcalin sont supportés dans des quantités de 2 à 25 % en masse et 0,1 à 15 % en masse, respectivement, par rapport à la quantité d'α-alumine.
PCT/JP2007/062190 2006-06-28 2007-06-11 Catalyseur pour reformage à la vapeur, appareil de production d'hydrogène, et système de pile à combustible Ceased WO2008001632A1 (fr)

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JP2008522440A JP5072841B2 (ja) 2006-06-28 2007-06-11 水蒸気改質用触媒、水素製造装置および燃料電池システム

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WO2011049130A1 (fr) * 2009-10-22 2011-04-28 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de production d'hydrogène et système de pile à combustible
JP2011088778A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 水素製造装置および燃料電池システム
JP2011088066A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 改質用触媒、改質装置および水素製造装置
JP2011206732A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置および燃料電池システム
JP2011210626A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 燃料電池システム
JP2011206726A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置及び燃料電池システム
JP2011210634A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 燃料電池システム
JP2011206725A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置及び燃料電池システム
JP2011206733A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置および燃料電池システム
WO2016088290A1 (fr) * 2014-12-01 2016-06-09 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Catalyseur de reformage à la vapeur pour gaz contenant des hydrocarbures, appareil de production d'hydrogène, et procédé de production d'hydrogène
WO2016143313A1 (fr) * 2015-03-09 2016-09-15 学校法人 工学院大学 CATALYSEUR DE REFORMAGE À LA VAPEUR POUR DES HYDROCARBURES, QUI EST OBTENU EN AMENANT UN COMPOSÉ 12SrO·7Al2O3 AYANT UNE STRUCTURE DE MAYENITE À PORTER DU Ru
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WO2011049130A1 (fr) * 2009-10-22 2011-04-28 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de production d'hydrogène et système de pile à combustible
JP2011088778A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 水素製造装置および燃料電池システム
JP2011088777A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 水素製造装置および燃料電池システム
JP2011088066A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 改質用触媒、改質装置および水素製造装置
JP2011206732A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置および燃料電池システム
JP2011210626A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 燃料電池システム
JP2011206726A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置及び燃料電池システム
JP2011210634A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 燃料電池システム
JP2011206725A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置及び燃料電池システム
JP2011206733A (ja) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp 水蒸気改質用触媒、水素製造装置および燃料電池システム
WO2016088290A1 (fr) * 2014-12-01 2016-06-09 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Catalyseur de reformage à la vapeur pour gaz contenant des hydrocarbures, appareil de production d'hydrogène, et procédé de production d'hydrogène
WO2016143313A1 (fr) * 2015-03-09 2016-09-15 学校法人 工学院大学 CATALYSEUR DE REFORMAGE À LA VAPEUR POUR DES HYDROCARBURES, QUI EST OBTENU EN AMENANT UN COMPOSÉ 12SrO·7Al2O3 AYANT UNE STRUCTURE DE MAYENITE À PORTER DU Ru
CN114471643A (zh) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 一种制氢的催化剂及其制备方法和应用
CN114471643B (zh) * 2020-10-27 2023-09-01 中国石油化工股份有限公司 一种制氢的催化剂及其制备方法和应用

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