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WO2007040097A1 - Catalyseur de reformage à la vapeur pour des hydrocarbures - Google Patents

Catalyseur de reformage à la vapeur pour des hydrocarbures Download PDF

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Publication number
WO2007040097A1
WO2007040097A1 PCT/JP2006/319062 JP2006319062W WO2007040097A1 WO 2007040097 A1 WO2007040097 A1 WO 2007040097A1 JP 2006319062 W JP2006319062 W JP 2006319062W WO 2007040097 A1 WO2007040097 A1 WO 2007040097A1
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WO
WIPO (PCT)
Prior art keywords
rare earth
earth metal
steam reforming
catalyst
alumina support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/319062
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English (en)
Japanese (ja)
Inventor
Yasuhito Ogawa
Yusuke Murakami
Nobuto Kobayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie Catalysts Japan Inc
Eneos Corp
Original Assignee
Japan Energy Corp
Sued Chemie Catalysts Japan Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Energy Corp, Sued Chemie Catalysts Japan Inc filed Critical Japan Energy Corp
Priority to JP2007538711A priority Critical patent/JP5107046B2/ja
Publication of WO2007040097A1 publication Critical patent/WO2007040097A1/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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
    • 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
    • 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
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group 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
    • C01B2203/12—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
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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 used for producing hydrogen from a hydrocarbon. More specifically, the present invention relates to a steam reforming catalyst that uses low-cost petroleum hydrocarbons such as LP gas, naphtha, gasoline, and kerosene that are widely distributed in the market as raw materials and steam reforms them to produce hydrogen. .
  • low-cost petroleum hydrocarbons such as LP gas, naphtha, gasoline, and kerosene that are widely distributed in the market as raw materials and steam reforms them to produce hydrogen.
  • a partial oxidation method or a water vapor reforming method is known, but the latter is considered more economical to produce hydrogen. ing.
  • a reforming catalyst is used for these hydrogen productions.
  • Nikkenore catalysts with nickel supported on a support such as alumina are known.
  • Power Nickel catalysts have a disadvantage that they cause a decrease in activity due to carbon deposition and have a low carbon number.
  • a large amount of hydrocarbon is used as a raw material, a large amount of steam is required to coexist, and the water vapor intensity increases the operating cost. Therefore, it is difficult to apply to petroleum-based hydrocarbons technically and economically. Is done.
  • noble metal catalysts using noble metals such as ruthenium and rhodium have attracted attention in recent years as reforming catalysts for hydrocarbons because they have an effect of suppressing carbon deposition and reduce the amount of water vapor used.
  • Examples include those in which ruthenium is supported on alumina (Non-patent Document 1), those in which ruthenium is supported on alumina or silica (Patent Document 1), and alumina containing alkaline earth metal aluminate and dinolecourea and ruthenium. Examples include those carrying components (Patent Document 2).
  • Non-Patent Document 2 ruthenium-based reforming catalysts are susceptible to catalyst poisoning due to sulfur contained in the raw material hydrocarbons (Non-Patent Document 2), and sulfur poisoning induces carbon deposition (Non-Patent Document 3). For this reason, it is difficult to make the carbon precipitation suppression effect function effectively. Therefore, when petroleum-based hydrocarbons are used as raw materials, the catalyst is required not only to have catalytic activity for reforming but also to suppress carbon deposition and suppress sulfur poisoning. In order to solve this problem, the conventional method has proposed the formation of a complex carrier or the addition of a third component.
  • a lanthanum oxide and cobalt supported as a cocatalyst on an alumina carrier supporting dinoleconia with zirconia sol as a precursor and containing ruthenium as an active ingredient Patent Document 3
  • Ila, IIla From the group consisting of oxides of lanthanoid metal oxides supported by a supported alumina composite containing norenium
  • Patent Document 4 Group 2 metals, Group 3 metals and Lanthanoid metal oxides
  • There have been proposed methods such as those obtained by reduction treatment (Patent Document 5) and those in which at least a ruthenium component, zirconium component and alkali metal component are supported on an alumina support (Patent Document 6).
  • Ru Ru.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 57-4232
  • Patent Document 2 Japanese Patent Application Laid-Open No. 5-220397
  • Patent Document 3 JP-A-7-88376
  • Patent Document 4 JP-A-8-52355
  • Patent Document 5 Japanese Patent Laid-Open No. 9-10586
  • Patent Document 6 Japanese Patent Laid-Open No. 2001-276624
  • Non-patent document 1 “Journal of the Fuel Society” 59 ⁇ 25 (1980)
  • Non-patent document 2 “Catalyst” 35 ⁇ 224 (1993)
  • Non-Patent Document 3 "Journal of Fuel Association” 68 pp. 39 (1989) Disclosure of the invention
  • the co-catalyst introduced into the catalyst and the composite alumina support function effectively, respectively, and can suppress carbon deposition and sulfur poisoning. Therefore, it is an object of the present invention to provide a steam reforming catalyst having excellent thermal stability that can maintain its catalytic function even when exposed to long-term use conditions in which high-temperature steam coexists.
  • the present inventors have conducted intensive research.
  • the alumina support containing a rare earth metal is selected from at least one compound selected from a ruthenium compound and a cobalt-rich compound.
  • a specific amount of rare earth metal is contained in the alumina support by the impregnation method, and 600 to 600 under an oxygen atmosphere before supporting the ruthenium compound and cobalt compound.
  • the added co-catalyst and composite carrier function synergistically with ruthenium to increase catalytic activity, and also suppress carbon deposition and suppress sulfur poisoning.
  • the present inventors have found a highly functional steam reforming catalyst that is not available in conventional catalysts, and have completed the present invention.
  • the present invention is as follows.
  • a steam reforming catalyst comprising an alumina support containing a rare earth metal and further supporting at least one compound selected from ruthenium compounds and at least one compound selected from cobalt compounds.
  • the rare earth metal is introduced into the alumina support by the impregnation method, and the amount of the rare earth metal is less than 8.5 a mol / m 2 with respect to the surface area of the alumina support, and at least one compound selected from the ruthenium compound and the cover.
  • a water vapor reforming catalyst obtained by calcining an alumina support containing the rare earth metal at 600 to 800 ° C. in the presence of oxygen before supporting at least one compound selected from the above-mentioned compounds.
  • the co-catalyst and the composite alumina support for suppressing carbon deposition and suppressing sulfur poisoning each function synergistically in an effective form and suitable arrangement with respect to ruthenium.
  • a steam reforming catalyst having excellent thermal stability that can maintain the catalytic function even when exposed to long-term use conditions in which high-temperature steam coexists.
  • FIG. 1 is a graph showing the results of Experiment 1 in which steam reforming was performed using the catalysts obtained in Examples 1-2 and Comparative Examples 1-4.
  • FIG. 2 is a graph showing the result of steam reforming by the method shown in Experiment 2.
  • the steam reforming catalyst of the present invention is one in which at least one compound selected from a ruthenium compound and a cobalt compound is supported on an alumina support containing a rare earth metal.
  • the impregnation method is used to contain the metal, the amount of the rare earth metal is less than 8.5 z mol / m 2 with respect to the surface area of the alumina support, and the oxygen atmosphere is supported before loading the ruthenium compound and the cobalt compound. It is important to fire at 600-800 ° C.
  • the alumina support is not particularly limited by the composition and structure, but the specific surface area is 60 m 2 / g so that the supported ruthenium and cobalt can be sufficiently dispersed. As described above, preferably, it is 80 to 120 m 2 / g, and the pore volume is 0.1 to 0.5 ml / g, preferably 0.2 to 0.5 ml / g. As an example, it is possible to use a material obtained by baking aluminum isopropoxide as a precursor and adding a pore-controlling organic material at 700 ° C or higher. Specific surface area and pore volume If it is smaller, the dispersibility of the supported ruthenium is deteriorated and the predetermined activity and catalyst life cannot be obtained. On the other hand, if it is larger than this, sufficient carrier strength cannot be obtained.
  • Examples of the shape of the alumina carrier include a spherical shape, a cylindrical shape, a prismatic shape, a tableting shape, a needle shape, a membrane shape, and a honeycomb structure.
  • molding the carrier for example, molding methods such as pressure molding, extrusion molding, rolling granulation molding, and press molding can be used. Any known method can be used without any particular limitation to limit the present invention.
  • rare earth metal By using the rare earth metal, the catalytic activity is increased and the catalyst life is improved.
  • rare earth metals lanthanum, cerium, praseodymium, neodymium, promethium, samarium, ytterbium, etc. can be used. In particular, lanthanum and cerium should be used. Any of these rare earth metals may be used alone or in combination of two or more. These rare earth metals can be used as precursors of rare earth metal compounds such as chlorides, nitrates and acetates in addition to oxides.
  • the alumina support containing the rare earth metal can be selectively distributed on the surface of the support by introducing the rare earth metal into the alumina support by an impregnation method.
  • an impregnation method By selectively distributing the rare earth metal on the alumina surface, a large effect can be obtained with a small amount of additive, and the mechanical strength and heat resistance of the carrier are improved by coating the alumina surface with the rare earth metal. .
  • rare earth metal is distributed inside the alumina support, and the rare earth metal distributed inside the alumina carrier is wasted, so that an effective addition effect (hereinafter referred to as an effect of addition amount) cannot be obtained.
  • the alumina support may be immersed in a solution containing the rare earth metal compound.
  • the solvent is preferably water.
  • the pore filling method is preferable.
  • the rare earth metal when the rare earth metal is introduced into the alumina support by the impregnation method and distributed on the surface of the support, it is important to coat the surface of the alumina with the rare earth metal so that the active metal can be in direct contact with the alumina. .
  • Rare earth metal covered the entire surface area of alumina support with a single layer
  • the amount of the rare earth metal contained in the alumina support is 8.5 x molZm 2 with respect to the surface area of the alumina support as its oxide. If the amount of rare earth metal exceeds 8.5 ⁇ molZm 2 , it cannot be distributed as a single layer on the surface of the alumina support, and the excess forms a multimolecular layer.
  • the amount of rare earth metal should be less than 8.5 ⁇ mol / m 2 with respect to the surface area of the alumina support so that the active metal can be in direct contact with the alumina.
  • the amount of rare earth metal is small, the effect of addition becomes low, which is not preferable. More preferably, it is 0 ⁇ 8 i mol / m 2 or more and less than 8.5 ⁇ mol / m 2 .
  • the amount of the rare earth metal contained in the alumina support can be adjusted to the above range by adjusting the concentration of the rare earth metal compound in the solution impregnated in the alumina support.
  • the rare earth metal is incorporated into the alumina support by the impregnation method, it is 600 to 800 ° C, preferably 650 to 750 ° C, more preferably 700 in the presence of oxygen before the ruthenium compound and the cobalt compound are incorporated. Calcination at ⁇ 750 ° C to fix rare earth metal as oxide to alumina support. Firing in the presence of oxygen may be performed in the air.
  • the firing temperature is lower than 600 ° C, the introduced rare earth metal is not stabilized on the support surface, and the alumina support becomes susceptible to deterioration due to the thermal history under the conditions of the steam reaction, and the temperature exceeds 800 ° C.
  • the introduced rare earth metal reacts with the alumina support to form a composite oxide (aluminate), and the specific surface area of the support is not only greatly impaired.
  • the distributed active metal ruthenium is not preferable because it does not function effectively.
  • a known impregnation method can be used as a method for supporting a ruthenium compound and a cobalt compound on the above-mentioned alumina support containing a rare earth metal.
  • a ruthenium compound a compound such as trisalt ruthenium or ruthenium nitrate can be used as a precursor of the ruthenium active ingredient. Particularly preferred is trisalt ruthenium (anhydride or hydrate).
  • the amount of ruthenium compound supported depends on the surface area of the support, but is generally a catalyst.
  • the metal content is 0.3 to 5.0% by weight, preferably 0.5 to 3.0% by weight based on the weight.
  • the cobalt compound serving as a cocatalyst can be supported on the support after the rare-earth metal is fixed as an oxide on the alumina support before or after the ruthenium compound is supported, or simultaneously with the ruthenium compound.
  • the cobalt compound is supported simultaneously with the noretenium compound, thereby enhancing the dispersibility of ruthenium and significantly improving the catalytic activity.
  • cobalt compound a compound such as cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt hydroxide, cobalt chloride and the like can be used as a precursor of the cobalt promoter component. Particularly preferably, cobalt nitrate is used.
  • Co / Ru ratio an atomic molar ratio to ruthenium
  • Co / Ru ratio an atomic molar ratio to ruthenium
  • the amount of cobalt in terms of an atomic molar ratio to ruthenium is 0 :! to 3, preferably ⁇ or 0.1 to 1.0, and more preferably 0.25 to 0.2. 5. If the Co / Rui force is less than SO.1, the cocatalyst effect does not sufficiently appear, and if it is 3 or more, excess cobalt adversely affects the catalytic function of ruthenium, which is not preferable.
  • the drying process and the baking process after supporting the ruthenium compound and the cobalt compound are not particularly defined for the conditions, but are performed, for example, in air at 100 ° C or higher.
  • the obtained catalyst may be subjected to reduction treatment in a liquid phase for the purpose of reducing the load such as pretreatment reduction when using the reforming reaction or heat generation at the initial stage of the reaction.
  • a 1-20% aqueous solution is prepared using a reducing agent such as formic acid, alkali metal salt of formic acid, honoremarin, hydrazine, sodium borohydride, etc., and the temperature is adjusted to room temperature to 60 ° C. After heating, add the catalyst.
  • the steam reforming catalyst obtained by the above method is preferably subjected to reduction treatment before the reforming reaction, but the reduction is performed as a result of contact with hydrogen in the reaction gas generated in the reforming reaction. Therefore, it is not always necessary.
  • the reduction temperature By controlling the reduction temperature, the catalyst performance is improved.
  • the reduction treatment it is carried out at 700 ° C or lower, preferably 600 to 700 ° C under hydrogen gas flow. If it exceeds 700 ° C, the dispersibility of ruthenium is lowered before the steam reforming reaction, and as a result, the catalyst performance is impaired.
  • the steam reforming catalyst of the present invention can be used in a process for producing hydrogen from hydrocarbons in the presence of steam. It can be applied to the production of hydrogen for hydrorefining at refineries, etc. where there are no particular restrictions on the application to the hydrogen production process, and the production of hydrogen for fuel cells in stationary distributed power sources.
  • the hydrocarbon is not particularly limited, for example, saturated aliphatic hydrocarbon compounds having 1 or more carbon atoms, such as methane, ethane, propane, butane, pentane, hexane, heptane, and octane, cyclopropane, cyclobutane, cyclopentane, Examples thereof include saturated alicyclic hydrocarbon compounds having 3 or more carbon atoms typified by cyclohexane and the like, and aromatic hydrocarbon compounds typified by benzene, toluene, xylene and the like. Petroleum fractions represented by LP gas, naphtha, gasoline, kerosene, light oil, etc.
  • the sulfur content in hydrocarbons is 0.2 ppm by weight or less, preferably 0.05 ppm by weight or less. If the sulfur content exceeds 0.2 ppm by weight, catalyst poisoning due to sulfur compounds becomes significant, and the catalyst activity decreases and the life of the catalyst tends to advance. Even for hydrocarbons with a sulfur content of more than 0.2 ppm by weight, pretreatment such as hydrodesulfurization or adsorptive desulfurization is performed before the reforming reaction, so that the sulfur content is less than 0.2 ppm by weight.
  • the steam reforming catalyst of the present invention can be used by reducing it to a low level. The lower the sulfur content of hydrocarbons in this pretreatment, the more preferable it is because catalyst poisoning by sulfur can be reduced.
  • the hydrocarbon reforming reaction performed using the steam reforming catalyst of the present invention has a steam / carbon ratio (hereinafter referred to as S / C ratio) of:! To 10, preferably 2 to 5. If the S / C ratio is less than 1, the decrease in the catalyst activity is remarkably accelerated, and if it is 10 or more, the steam unit supplied is excessive, resulting in an increase in cost.
  • the reaction temperature depends on the type of hydrocarbon, but is usually 400 to 800 ° C, preferably 500 to 750 ° C. Even if the reaction temperature is less than 400 ° C, the steam reforming reaction proceeds, but the ratio of hydrogen generated thermodynamically decreases and the hydrogen yield decreases, which is preferable. If the temperature exceeds 800 ° C, the thermal degradation will accelerate and the catalyst life will be significant. It is not preferable because it decreases.
  • the reaction system using the steam reforming catalyst of the present invention is not particularly limited, such as a continuous flow system or a batch system, but is preferable because the former can efficiently perform the reforming reaction.
  • Liquid hourly space velocity of hydrocarbons in this case (hereinafter, LHSV) is the force usually 10 hr _ 1 below also depend on the type of hydrocarbon, preferably 5 hr _1 below. Possible reforming reaction even L HSV exceeds the 10 hr _ 1 depending on the type of hydrocarbons, but economically preferable because it is necessary to plant capacity to supply a large amount of hydrocarbon and steam.
  • the reaction pressure depends on the type of hydrocarbon and is usually 0 to 5 MPa, preferably 0 to 2 MPa. If the reaction pressure exceeds 5 MPa, equipment using expensive pressure-resistant materials is required, which is not economically preferable.
  • the reaction mode using the steam reforming catalyst of the present invention is not particularly limited, such as a fixed bed type, a moving bed type, and a fluidized bed type.
  • the reactor using the steam reforming catalyst of the present invention is not particularly limited.
  • the steam reforming catalyst of the present invention can be used alone or in combination with other catalysts.
  • a catalyst B was obtained in the same manner as in Example 1 except that cobalt nitrate was not used in the method of Example 1.
  • Comparative Example 2 (Catalyst C)
  • a catalyst C was obtained in the same manner as in Example 1 except that lanthanum nitrate was not used in the method of Example 1.
  • catalyst D was prepared by the same preparation method as in Example 1 except that the calcination treatment after supporting lanthanum nitrate was performed at 850 ° C. for 3 hours in the presence of oxygen. .
  • a catalyst E was obtained in the same manner as in Example 1 except that 35.3 g of lanthanum nitrate hexahydrate was used in the method of Example 1.
  • a catalyst F was obtained in the same manner as in Example 1, except that 147 g of lanthanum nitrate hexahydrate was used in the method of Example 1.
  • Table 1 shows the compositions measured by IPC mass spectrometry and the specific surface areas obtained by the nitrogen adsorption method for the catalysts A to F obtained by the above preparation.
  • FIG. 1 shows the results of the steam reforming reaction carried out under the above-mentioned conditions using the catalysts obtained in! -2 and Comparative Examples 1-4.
  • Catalyst A and Catalyst E obtained according to the present invention have a higher C1 conversion rate and higher activity than when the catalysts of Comparative Examples 1 to 4 are used, and maintain a high conversion rate even after a lapse of time. It can be seen that the catalyst is less deteriorated.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un catalyseur de reformage à la vapeur ayant une activité élevée et une longue durée de vie, lequel permet de produire efficacement de l'hydrogène en utilisant un hydrocarbure comme matière première. L'invention concerne précisément un catalyseur de reformage à la vapeur obtenu en chargeant un support en alumine, lequel a été traité pour faire en sorte qu'il contienne un métal des terres rares, avec au moins un composé sélectionné parmi des composés du ruthénium et au moins un composé sélectionné parmi des composés du cobalt. Ce catalyseur de reformage à la vapeur est caractérisé en ce que le métal des terres rares est introduit dans le support en alumine par imprégnation et en ce que la quantité du métal des terres rares est inférieure à 8,5 μmol/m2 par rapport à la surface du support en alumine. Le catalyseur de reformage à la vapeur est en outre caractérisé en ce que le support en alumine contenant le métal des terres rares est calciné à 600-800°C en présence d'oxygène avant de charger l'au moins un composé sélectionné parmi des composés du ruthénium et l'au moins un composé sélectionné parmi des composés du cobalt.
PCT/JP2006/319062 2005-09-30 2006-09-26 Catalyseur de reformage à la vapeur pour des hydrocarbures Ceased WO2007040097A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009254929A (ja) * 2008-04-14 2009-11-05 Japan Energy Corp 低温での水素製造に適した水素製造用改質触媒、及び該触媒を用いた水素製造方法
JP2011167595A (ja) * 2010-02-16 2011-09-01 Jx Nippon Oil & Energy Corp 水素製造用改質触媒及びその製造方法、並びに該触媒を用いた水素製造方法

Citations (5)

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