WO2012115193A1 - Catalyseur de reformage de dioxyde de carbone pour des hydrocarbures et procédé de reformage de dioxyde de carbone pour des hydrocarbures - Google Patents

Catalyseur de reformage de dioxyde de carbone pour des hydrocarbures et procédé de reformage de dioxyde de carbone pour des hydrocarbures Download PDF

Info

Publication number
WO2012115193A1
WO2012115193A1 PCT/JP2012/054431 JP2012054431W WO2012115193A1 WO 2012115193 A1 WO2012115193 A1 WO 2012115193A1 JP 2012054431 W JP2012054431 W JP 2012054431W WO 2012115193 A1 WO2012115193 A1 WO 2012115193A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon dioxide
catalyst
site
dioxide reforming
reforming
Prior art date
Application number
PCT/JP2012/054431
Other languages
English (en)
Japanese (ja)
Inventor
佐藤秀人
Original Assignee
株式会社村田製作所
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 株式会社村田製作所 filed Critical 株式会社村田製作所
Priority to JP2013501121A priority Critical patent/JP5626446B2/ja
Publication of WO2012115193A1 publication Critical patent/WO2012115193A1/fr

Links

Images

Classifications

    • 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
    • B01J23/78—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 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
    • C01B2203/02—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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • 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
    • 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
    • Y02P20/141—Feedstock
    • 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 hydrocarbon carbon dioxide reforming catalyst used for producing a synthesis gas containing hydrogen and carbon monoxide by reforming a hydrocarbon-based source gas, and a hydrocarbon using the same.
  • the present invention relates to a carbon dioxide reforming method.
  • hydrocarbon gases are generated in technical fields such as petroleum refining and petrochemistry, but they are not necessarily efficiently used as raw material gases for various substances, and a method for converting them into more effective substances is required. Yes.
  • hydrocarbon gas reforming hydrocarbon steam reforming, saturated carbonization are methods for producing synthesis gas containing hydrogen and carbon monoxide by reforming hydrocarbon-based gas.
  • hydrocarbon-based gas There are known methods such as combined reforming of carbon dioxide and steam in which both carbon dioxide and steam react with hydrogen in the presence of a catalyst.
  • Carbon dioxide reforming of hydrocarbons is suitable for producing a synthesis gas having a relatively high carbon monoxide concentration by reacting a saturated hydrocarbon such as methane with carbon dioxide in the presence of a catalyst.
  • steam reforming of hydrocarbons is suitable for producing a synthesis gas having a relatively high hydrogen concentration by reacting a saturated hydrocarbon such as methane with steam in the presence of a catalyst.
  • carbon may be deposited on the catalyst during the process of hydrocarbon decomposition.
  • the degree of carbon deposition varies depending on the hydrocarbon reforming conditions. It is said that carbon is most likely to precipitate in carbon dioxide reforming of hydrocarbons, and that the amount of carbon deposition is relatively small in hydrocarbon steam reforming.
  • the carbon deposited on the catalyst gradually accumulates to reduce the catalytic activity, and if it is deposited in large quantities, the reaction tube may be clogged.
  • hydrocarbon ratio hereinafter, “steam / hydrocarbon ratio” is set high, and carbon deposition is suppressed by introducing excessive steam.
  • the hydrocarbon carbon dioxide or steam reforming catalyst includes a nickel-based catalyst in which nickel is supported on a substrate such as alumina, a ruthenium-based catalyst in which ruthenium is supported (see Patent Document 1), and further, such as alumina.
  • a rhodium-based catalyst in which rhodium is supported on a substrate is known.
  • rhodium, cobalt, and nickel are supported as active components on a carrier using lanthanum aluminate, strontium titanate, and barium titanate, which are perovskite compounds, for the purpose of suppressing carbon deposition and improving activity at low temperatures.
  • a carrier using lanthanum aluminate, strontium titanate, and barium titanate, which are perovskite compounds, for the purpose of suppressing carbon deposition and improving activity at low temperatures.
  • Such a catalyst is known (see Patent Document 3).
  • Nickel-based catalysts in which nickel is supported on a substrate such as alumina, which is common as a hydrocarbon steam reforming catalyst, are likely to cause carbon deposition on the catalyst. Therefore, there is a need to carry out a hydrocarbon steam reforming reaction under conditions of a high steam / hydrocarbon ratio with excess steam.
  • excess water vapor has the problem of increased energy consumption during the water vaporization process, and the concentration of carbon monoxide in the synthesis gas composition to be produced decreases, resulting in monoxide oxidation such as fuel synthesis.
  • it is not suitable for applications that require synthesis gas with a high carbon concentration.
  • this is a reforming reaction that is more likely to cause carbon deposition.
  • the ruthenium-based catalyst as shown in Patent Document 1 has an action of suppressing carbon deposition, carbon deposition is less than that of a nickel-based catalyst and the activity can be easily maintained.
  • unsaturated hydrocarbons coexist in the raw material, thermal carbon deposition and activity decrease are likely to occur, and even if the ruthenium-based catalyst has an effect of suppressing carbon deposition, it may be caused by unsaturated hydrocarbons contained in the raw material gas. There is a problem that poisoning and activity decrease.
  • the rhodium-based catalyst in which rhodium is supported on a substrate such as alumina as shown in Patent Document 2 is said to have similar problems.
  • Patent Document 3 since a catalyst using a perovskite type complex oxide as shown in Patent Document 3 has high activity, it is possible to suppress carbon deposition even if the amount of steam supplied is reduced in steam reforming. However, it has not yet been possible to suppress carbon deposition in carbon dioxide reforming where carbon deposition is more likely to occur.
  • the present invention solves the above problems, and efficiently reforms hydrocarbons with carbon dioxide while suppressing carbon deposition (for example, reforming methane to carbon dioxide to produce hydrogen and carbon monoxide. It is an object of the present invention to provide a hydrocarbon carbon dioxide reforming catalyst and a hydrocarbon carbon dioxide reforming method using the same.
  • the hydrocarbon carbon dioxide reforming catalyst of the present invention comprises: Complex oxide ABO 3 having a perovskite structure (the element constituting the A site is mainly Sr and may contain Ba, Ca, Mg, and the element constituting the B site is mainly Ti and may contain Zr) A catalyst containing Ni, (a) molar ratio of the total amount of elements constituting the A site and the total amount of elements constituting the B site: A / B is in the range of 0.90 ⁇ A / B ⁇ 1.20, (b) A molar ratio of the total amount of Ni and the elements constituting the B site: Ni / B is in a range of 0.02 ⁇ Ni / B ⁇ 0.16.
  • the hydrocarbon carbon dioxide reforming catalyst according to claim 2 comprises: (a) molar ratio of the total amount of elements constituting the A site and the total amount of elements constituting the B site: A / B is in the range of 0.90 ⁇ A / B ⁇ 1.20, (b) The molar ratio of the total amount of Ni and the elements constituting the B site: Ni / B is in the range of 0.04 ⁇ Ni / B ⁇ 0.16.
  • the hydrocarbon carbon dioxide reforming catalyst according to claim 3 is: (a) The molar ratio of the total amount of elements constituting the A site and the total amount of elements constituting the B site: A / B is in the range of 0.96 ⁇ A / B ⁇ 1.20, (b) The molar ratio of the total amount of Ni and the elements constituting the B site: Ni / B is in the range of 0.04 ⁇ Ni / B ⁇ 0.13.
  • the hydrocarbon carbon dioxide reforming catalyst according to claim 4 (a) The molar ratio of the total amount of elements constituting the A site and the total amount of elements constituting the B site: A / B is in the range of 0.98 ⁇ A / B ⁇ 1.20, (b) A molar ratio of the total amount of Ni and the elements constituting the B site: Ni / B is in the range of 0.04 ⁇ Ni / B ⁇ 0.08.
  • the hydrocarbon carbon dioxide reforming catalyst according to claim 5 (a) The molar ratio of the total amount of elements constituting the A site and the total amount of elements constituting the B site: A / B is in the range of 0.98 ⁇ A / B ⁇ 1.01, (b) A molar ratio of the total amount of Ni and the elements constituting the B site: Ni / B is in the range of 0.04 ⁇ Ni / B ⁇ 0.08.
  • the hydrocarbon carbon dioxide reforming catalyst according to claim 6 (a) The molar ratio of the total amount of elements constituting the A site and the total amount of elements constituting the B site: A / B is in the range of 1.01 ⁇ A / B ⁇ 1.04, (b) The molar ratio of the total amount of Ni and the B site element: Ni / B is in the range of 0.08 ⁇ Ni / B ⁇ 0.12.
  • the hydrocarbon carbon dioxide reforming catalyst according to claim 7 is characterized in that at least a part of the Ni is dissolved in the composite oxide ABO 3 .
  • the hydrocarbon carbon dioxide reforming method according to claim 8 uses the hydrocarbon carbon dioxide reforming catalyst according to any one of claims 1 to 7 as a raw material gas comprising hydrocarbon and carbon dioxide. Then, reforming is performed to produce a synthesis gas composed of hydrogen and CO.
  • the carbon dioxide is efficiently reformed with carbon dioxide while suppressing carbon deposition (for example, methane is reformed with carbon dioxide to generate hydrogen and carbon monoxide). It becomes possible to provide a catalyst for carbon dioxide reforming of a possible hydrocarbon. Specifically, for example, when carbon dioxide reforming is performed at 900 ° C., a hydrocarbon carbon dioxide reforming catalyst capable of sufficiently suppressing carbon deposition can be provided.
  • Ni In order for the carbon dioxide reforming catalyst of the present invention to function effectively in the carbon dioxide reforming of hydrocarbons, Ni must be at least partially reduced to metallic Ni, in producing the carbon dioxide reforming catalyst of the present invention, for example, NiO can be used as the Ni raw material. In that case, when the catalyst is used for carbon dioxide reforming, it can be made into an effective state as a catalyst for carbon dioxide reforming by performing a reduction treatment and reducing at least a part of Ni to metal Ni. .
  • a carbon dioxide reforming catalyst capable of reforming hydrocarbons with carbon dioxide extremely efficiently without substantially depositing carbon. Become. Specifically, for example, when carbon dioxide reforming is performed at 800 ° C., a carbon dioxide reforming catalyst capable of reforming hydrocarbons with carbon dioxide extremely efficiently while preventing carbon precipitation almost completely. It becomes possible to provide.
  • the carbon dioxide capable of reforming hydrocarbons with carbon dioxide more efficiently than the carbon dioxide reforming catalyst of claim 4 without substantially depositing carbon It becomes possible to provide a carbon reforming catalyst.
  • the catalyst is heated at a higher temperature than the reforming temperature range in order to suppress thermal contraction, surface area variation, cracking and cracking of the catalyst due to thermal shock in the reforming temperature range. Even when calcined with, the carbon deposition of the catalyst and the activity of the catalyst are not reduced. Therefore, it is possible to provide a carbon dioxide reforming catalyst capable of reforming hydrocarbons with carbon dioxide more efficiently.
  • the Ni component is preferably dissolved in the composite oxide ABO 3 having a perovskite structure, and the Ni oxide is a composite oxide in which most of the Ni component is a support.
  • [1] Manufacture of carbon dioxide reforming catalyst (1) Manufacture of catalyst 1 of Table 1 As catalyst raw materials, strontium carbonate (SrCO 3 ), titanium oxide (TiO 2 ), and nickel oxide (NiO) are prepared.
  • strontium carbonate (SrCO 3 ), titanium oxide (TiO 2 ), and nickel oxide (NiO) are prepared.
  • the carbon dioxide reforming catalyst (hereinafter also simply referred to as “catalyst”) 1 is a catalyst as a comparative example in which the above-mentioned A / B (molar ratio) does not satisfy the requirements of the present invention.
  • Catalysts (carbon dioxide reforming catalysts) 2 to 16 were produced.
  • Each of the catalysts 2 to 16 is a catalyst in which the above-mentioned values of A / B (molar ratio) and Ni / B (molar ratio) satisfy the requirements of the present invention.
  • the gas discharged from the outlet 5 of the reaction tube 1 was introduced into the analyzer and the gas concentration was measured.
  • the catalyst indicated by reference numeral 3 in FIG. 1 is taken out from the reaction tube 1, and the amount of carbon deposited in the carbon dioxide reforming test over 75 hours is calculated from the difference in catalyst weight before and after the test. Asked.
  • the carbon dioxide reforming test of methane (CH 4 ) was also performed under the condition of reforming temperature: 800 ° C., where carbon deposition is more likely to occur than the reforming temperature: 900 ° C.
  • the reforming test at a reforming temperature of 800 ° C. is performed by filling 2 cc of the catalyst after the carbon dioxide reforming test at 900 ° C. for 75 hours into the reaction tube 1 and setting the temperature to 800 ° C. by the heater 2.
  • the catalyst is taken out from the reaction tube 1 and the amount of carbon deposited in the carbon dioxide reforming test at 800 ° C. for 6 hours is calculated from the catalyst weight difference before and after the reforming test at 800 ° C. Asked.
  • Reforming temperature outlet methane concentration in reforming test at 900 ° C.
  • reforming temperature 900 ° C.
  • reforming temperature 800 ° C.
  • Table 1 shows the amount of deposited carbon.
  • Ni / B value is smaller, the carbon deposition resistance is higher. It was confirmed that there was a tendency.
  • the carbon deposition resistance and catalytic activity of the hydrocarbon carbon dioxide reforming catalyst is not only the Ni content, that is, the Ni / B value, but also the composite oxidation having the perovskite structure as the support. It also varies greatly depending on the composition of the product ABO 3 , that is, the A / B value. Therefore, in order to obtain a catalyst having high carbon deposition resistance and excellent catalytic activity, both “composition of composite oxide ABO 3 as support: A / B value” and “Ni content: Ni / B value” It is important to set to an appropriate range.
  • the composition range defined in claim 1 of the present invention that is, “0.90 ⁇ A / B ⁇ 1.20 and 0.02 ⁇ Ni / B ⁇ 0.16”
  • the above-mentioned “carbon deposition amount” after the carbon dioxide reforming test at 900 ° C. for 75 hours is 1 wt% or less
  • the catalyst in the composition range defined in claim 1 is, for example, 1000 ° C. or more. This is significant when applied to applications in which carbon dioxide reforming of hydrocarbons is performed under the following temperature conditions.
  • composition range where the Ni / B value is small that is, a composition range where the Ni content is low
  • the catalytic activity is low, so that sufficient catalytic activity is required in addition to excellent carbon deposition resistance.
  • the composition range defined in claim 2 of the present invention that is, “0.90 ⁇ A / B ⁇ 1.20 and 0.04 ⁇ Ni / B ⁇ 0.16” It is preferable to set it as the composition range.
  • composition range defined in claim 3 of the present invention that is, “0.96 ⁇ A / B ⁇ 1.20 and 0.04 ⁇ Ni / B ⁇ 0.13”
  • carbon deposition amount after the carbon dioxide reforming test at 900 ° C. for 75 hours is 0 wt%
  • the catalyst in the composition range defined in claim 3 is, for example, 900 ° C. or more. It is considered effective to be applied to applications in which hydrocarbons undergo carbon dioxide reforming under temperature conditions.
  • composition range defined in claim 4 of the present invention i.e. “0.98 ⁇ A / B ⁇ 1.20 and 0.04 ⁇ Ni / B ⁇ 0.08”
  • carbon deposition amount after the carbon dioxide reforming test at 800 ° C. for 6 hours is 0 wt%
  • the catalyst in the composition range defined in claim 4 is, for example, 800 ° C. or more. It is considered effective to be applied to applications in which hydrocarbons undergo carbon dioxide reforming under temperature conditions.
  • the composition range defined in claim 5 of the present invention i.e. “0.98 ⁇ A / B ⁇ 1.01 and 0.04 ⁇ Ni / B ⁇ 0.08” It is preferable that the composition range be
  • catalysts 17 to 21 shown in Table 2.
  • Each of the catalysts 17 to 21 is a catalyst that satisfies the requirements of the present invention in the values of A / B (molar ratio) and Ni / B (molar ratio) described above.
  • Carbon dioxide reforming test The carbon dioxide reforming test for hydrocarbons (methane (CH4) in this example) was conducted using the above-described reduction-treated carbon dioxide reforming catalyst, and the characteristics were examined.
  • the gas discharged from the outlet 5 of the reaction tube 1 was introduced into the analyzer and the gas concentration was measured.
  • the catalyst indicated by reference numeral 3 in FIG. 1 is taken out from the reaction tube 1, and the amount of carbon deposited in the carbon dioxide reforming test over 50 hours is calculated from the difference in catalyst weight before and after the test. Asked.
  • Table 2 shows the outlet methane concentration in the reforming test at the reforming temperature: 900 ° C. and the carbon deposition amount in the reforming test at the reforming temperature: 900 ° C. for 50 hours.
  • the composition range defined in claim 6 of the present invention that is, In the composition range of “1.01 ⁇ A / B ⁇ 1.04 and 0.08 ⁇ Ni / B ⁇ 0.12,” the above-mentioned “carbon precipitation” after the carbon dioxide reforming test at 900 ° C. for 50 hours.
  • the amount ” is 2 wt% or less, and the catalyst having the composition range defined in claim 6 is significant when applied to an application in which carbon dioxide reforming of hydrocarbon is performed at a temperature condition of, for example, 1000 ° C. or more. .
  • Example 2 since the firing temperature of the catalyst is 1300 ° C., the thermal strength of the catalyst is improved as compared with Example 1. Therefore, the present invention is effective for applications in which carbon dioxide reforming of hydrocarbons is performed under a high reforming temperature condition of 900 ° C. or higher.
  • the progress of the sintering may cause a decrease in the surface area and agglomeration of the metal component, thereby reducing the carbon deposition resistance and activity of the catalyst.
  • the composition is in the range of claim 6 of the present invention, the carbon deposition of the catalyst and the activity of the catalyst are not reduced.
  • the element constituting the A site is Sr and the element constituting the B site is Ti as an example of the composite oxide ABO 3 having a perovskite structure has been described.
  • the additive that substitutes Sr or Ti at the B site and the impurities that are mixed without intentional addition.
  • an element that enters the A site of the composite oxide ABO 3 having a perovskite structure for example, Ba, Ca, Mg substitutes Sr in SrTiO 3 and acts in the same manner as Sr. There is no problem that Ba, Ca, and Mg are present as impurities.
  • an element entering the B site of the composite oxide ABO 3 having a perovskite structure for example, Zr replaces Ti in SrTiO 3 and acts in the same way as Ti, so that it can be used as an additive or impurity in the catalyst. There is no problem that Zr exists.
  • A is the total number of moles of Sr, Ba, Ca, Mg” and “B is the total number of moles of Ti and Zr”, and A / B and Ni / By selecting the value of B, it is possible to obtain the same carbon deposition suppression effect as in this example.
  • the Sr content in the element contained in the A site and the Ti content in the element contained in the B site are each desirably 90 mol% or more.
  • the present invention is also meaningful in solving the problem of instability of the carbon dioxide reforming catalyst caused by such impurities.
  • the specific surface area is not particularly limited, but the catalytic activity tends to improve as the specific surface area increases. Therefore, the specific surface area is usually 1 m 2 / g or more. It is preferable to have.
  • the specific surface area of the carbon dioxide reforming catalyst of the present invention is usually , 6 m 2 / g or less is preferable.
  • NiO is reduced to metal Ni by heat treatment in an atmosphere gas containing hydrogen
  • NiO can be converted to metal by heat treatment in another reducing atmosphere. Needless to say, it may be configured to reduce to Ni.
  • the hydrocarbon to be carbon dioxide reformed is methane (CH 4 ).
  • hydrocarbons other than methane such as butane and propane are used.
  • the present invention can also be applied when carbon dioxide is reformed.
  • the present invention is not limited to the above-mentioned examples in other respects.
  • Various conditions are included within the scope of the invention regarding specific conditions for producing the carbon dioxide reforming catalyst of the present invention. It is possible to add applications and modifications.

Abstract

L'invention concerne un catalyseur de reformage de dioxyde de carbone pour des hydrocarbures, permettant le reformage efficace de dioxyde de carbone en hydrocarbures tout en supprimant la précipitation du carbone (par exemple dans le cas du reformage du méthane par du dioxyde de carbone pour produire de l'hydrogène et du monoxyde de carbone). L'invention concerne également un procédé de reformage de dioxyde de carbone pour des hydrocarbures au moyen dudit catalyseur. Le catalyseur de reformage de dioxyde de carbone pour des hydrocarbures contient un oxyde complexe ABO3 présentant une structure pérovskite (l'élément qui constitue le site A est du Sr, et peut partiellement contenir du B, du Ca ou du Mg ; l'élément qui constitue le site B est du Ti, et peut partiellement contenir du Zr), et du Ni ; (a) le rapport molaire A/B entre la quantité totale des éléments qui constituent le site A et la quantité totale des éléments qui constituent le site B se situe dans une plage de 0,90 ≦ A/B ≦ 1,20 et (b) le rapport molaire Ni//B entre les quantités totales des éléments qui constituent le site B et le Ni se situe dans une plage de 0,02 ≦ Ni/B ≦ 0,16.
PCT/JP2012/054431 2011-02-25 2012-02-23 Catalyseur de reformage de dioxyde de carbone pour des hydrocarbures et procédé de reformage de dioxyde de carbone pour des hydrocarbures WO2012115193A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013501121A JP5626446B2 (ja) 2011-02-25 2012-02-23 炭化水素の二酸化炭素改質用触媒および炭化水素の二酸化炭素改質方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-039609 2011-02-25
JP2011039609 2011-02-25

Publications (1)

Publication Number Publication Date
WO2012115193A1 true WO2012115193A1 (fr) 2012-08-30

Family

ID=46720967

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/054431 WO2012115193A1 (fr) 2011-02-25 2012-02-23 Catalyseur de reformage de dioxyde de carbone pour des hydrocarbures et procédé de reformage de dioxyde de carbone pour des hydrocarbures

Country Status (2)

Country Link
JP (1) JP5626446B2 (fr)
WO (1) WO2012115193A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014189006A1 (fr) * 2013-05-21 2014-11-27 株式会社村田製作所 Catalyseur de reformation d'un gaz hydrocarboné et procédé de reformation d'un gaz hydrocarboné au moyen dudit catalyseur

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06182201A (ja) * 1984-07-31 1994-07-05 Hitachi Ltd 高温で安定な触媒及びその調製法ならびにその触媒を用いて化学反応を実施する方法
JP2006346598A (ja) * 2005-06-16 2006-12-28 Nissan Motor Co Ltd 水蒸気改質触媒
JP2007523737A (ja) * 2003-04-29 2007-08-23 エイチアールディー コーポレイション ペロブスカイトベースの触媒、その調整、およびメタンからエチレンへの転化のためのその使用
WO2008084785A1 (fr) * 2007-01-09 2008-07-17 Murata Manufacturing Co., Ltd. Catalyseur de reformage de dioxyde de carbone et son procédé de production de celui-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06182201A (ja) * 1984-07-31 1994-07-05 Hitachi Ltd 高温で安定な触媒及びその調製法ならびにその触媒を用いて化学反応を実施する方法
JP2007523737A (ja) * 2003-04-29 2007-08-23 エイチアールディー コーポレイション ペロブスカイトベースの触媒、その調整、およびメタンからエチレンへの転化のためのその使用
JP2006346598A (ja) * 2005-06-16 2006-12-28 Nissan Motor Co Ltd 水蒸気改質触媒
WO2008084785A1 (fr) * 2007-01-09 2008-07-17 Murata Manufacturing Co., Ltd. Catalyseur de reformage de dioxyde de carbone et son procédé de production de celui-ci

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014189006A1 (fr) * 2013-05-21 2014-11-27 株式会社村田製作所 Catalyseur de reformation d'un gaz hydrocarboné et procédé de reformation d'un gaz hydrocarboné au moyen dudit catalyseur

Also Published As

Publication number Publication date
JP5626446B2 (ja) 2014-11-19
JPWO2012115193A1 (ja) 2014-07-07

Similar Documents

Publication Publication Date Title
Boukha et al. Behaviour of Rh supported on hydroxyapatite catalysts in partial oxidation and steam reforming of methane: on the role of the speciation of the Rh particles
Franchini et al. Ce-substituted LaNiO3 mixed oxides as catalyst precursors for glycerol steam reforming
JP5126560B2 (ja) 炭化水素系ガス改質触媒、その製造方法および、合成ガスの製造方法
JP6187282B2 (ja) 炭化水素改質触媒
Fang et al. Highly active and stable Ni/Y2Zr2O7 catalysts for methane steam reforming: On the nature and effective preparation method of the pyrochlore support
JP5327323B2 (ja) 炭化水素系ガス改質用触媒、その製造方法、および合成ガスの製造方法
WO2011065194A1 (fr) Catalyseur de réaction anti-conversion catalytique, et procédé de production de gaz synthétique utilisant ce catalyseur
US11958746B2 (en) Hydrocarbon reforming catalyst and hydrocarbon reforming apparatus
Silva et al. Hydrogen production through steam reforming of toluene over Ni supported on MgAl mixed oxides derived from hydrotalcite-like compounds
Nuvula et al. Selective substitution of Ni by Ti in LaNiO3 perovskites: A parameter governing the oxy-carbon dioxide reforming of methane
Bkour et al. Nickel nanoparticles supported on silica for the partial oxidation of isooctane
Izadi et al. Preparation of highly stable bimetallic ni–cu catalyst for simultaneous production of hydrogen and fish-bone carbon nanofibers: Optimization, effect of catalyst preparation methods and deactivation
Kikuchi et al. Novel nickel catalysts based on spinel-type mixed oxides for methane and propane steam reforming
Bai et al. Design of Ni‐substituted La2 (CeZrNi) 2O7 pyrochlore catalysts for methane dry reforming
JP5626446B2 (ja) 炭化水素の二酸化炭素改質用触媒および炭化水素の二酸化炭素改質方法
Liu et al. Ni/Ce1− xMx catalyst generated from metallo-organic network for autothermal reforming of diesel surrogate
WO2013187436A1 (fr) Catalyseur de reformage, son procédé de préparation et procédé de fabrication d'un gaz de synthèse
JP7318734B2 (ja) 炭化水素改質触媒および炭化水素改質装置
JP7347541B2 (ja) 炭化水素改質触媒、炭化水素改質装置、および、炭化水素改質触媒の硫黄劣化回復方法
US11628426B2 (en) Catalyst for chemical looping combustion
WO2014189006A1 (fr) Catalyseur de reformation d'un gaz hydrocarboné et procédé de reformation d'un gaz hydrocarboné au moyen dudit catalyseur
US20220105495A1 (en) Hydrocarbon reforming catalyst and hydrocarbon reforming apparatus
JP2015229125A (ja) 炭化水素改質触媒の前処理方法、炭化水素改質触媒、および炭化水素改質方法
JP5479307B2 (ja) 触媒及び改質ガスの製造方法
CN114829003A (zh) 烃重整催化剂和烃重整装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12749704

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013501121

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12749704

Country of ref document: EP

Kind code of ref document: A1