CA2864063C - Hexaaluminate-comprising catalyst for the reforming of hydrocarbons and a reforming process - Google Patents

Hexaaluminate-comprising catalyst for the reforming of hydrocarbons and a reforming process Download PDF

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Publication number
CA2864063C
CA2864063C CA2864063A CA2864063A CA2864063C CA 2864063 C CA2864063 C CA 2864063C CA 2864063 A CA2864063 A CA 2864063A CA 2864063 A CA2864063 A CA 2864063A CA 2864063 C CA2864063 C CA 2864063C
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mol
catalyst
range
hexaaluminate
further preferably
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CA2864063A
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French (fr)
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CA2864063A1 (en
Inventor
Stephan Schunk
Andrian Milanov
Andreas Strasser
Guido WASSERSCHAFF
Thomas Roussiere
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BASF SE
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BASF SE
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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
    • B01J23/76—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/83—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 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
    • 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
    • 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
    • B01J23/8946—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 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/737—Hexaaluminate-type AB12O19
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—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
    • C01B2203/1241—Natural gas or methane
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The present invention relates to a hexaaluminate-containing catalyst, which comprises a hexaaluminate-containing phase that includes cobalt and at least one additional element from the group La, Ba, Sr. The Co content of the hexaaluminate-containing catalyst is in the range of 2-15 mol%, preferably 3-10 mol% and further preferably in the range of 4-8 mol%, the content of the at least one additional element from the group La, Ba, Sr is in the range of 2-25 mol%, preferably 3-15 mol%, further preferably 4-10 mol% and the content of Al is in the range of 70-90 mol%. In addition to the hexaaluminate-containing phase, the catalyst can include a 0-50 wt% oxide secondary phase, the portion of oxide secondary phase preferably in the range of 3-40 wt% and further preferably in the range of 5-30 wt%. The method according to the invention for producing the catalyst is based on initially bringing a source of aluminium oxide, preferably, a boehmite, into contact with cobalt species and at least one element from the group La, Ba, Sr. The moulded and dried material is preferably calcined at a temperature greater than or equal to 800°C. The reforming method for converting hydrocarbons, preferably methane, in the presence of CO2 is characterised in that the catalyst is used at a process temperature greater than 700°C, preferably greater than 800°C and further preferably greater than 900°C, the process pressure being greater than 5 bar, preferably greater than 10 bar and further preferably greater than 15 bar.
CA2864063A 2012-02-10 2013-02-07 Hexaaluminate-comprising catalyst for the reforming of hydrocarbons and a reforming process Active CA2864063C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12154901.8 2012-02-10
EP12154901 2012-02-10
PCT/IB2013/051024 WO2013118078A1 (en) 2012-02-10 2013-02-07 Hexaaluminate-comprising catalyst for reforming of hydrocarbons and reforming process

Publications (2)

Publication Number Publication Date
CA2864063A1 CA2864063A1 (en) 2013-08-15
CA2864063C true CA2864063C (en) 2021-06-01

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Family Applications (1)

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CA2864063A Active CA2864063C (en) 2012-02-10 2013-02-07 Hexaaluminate-comprising catalyst for the reforming of hydrocarbons and a reforming process

Country Status (9)

Country Link
EP (1) EP2812111B1 (en)
JP (1) JP6238909B2 (en)
KR (1) KR20140126366A (en)
CN (1) CN104080530B (en)
CA (1) CA2864063C (en)
DK (1) DK2812111T3 (en)
RU (1) RU2631497C2 (en)
WO (1) WO2013118078A1 (en)
ZA (1) ZA201406561B (en)

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EP2886514A1 (en) 2013-12-20 2015-06-24 Basf Se Method for reforming mixtures of hydrocarbons and carbon dioxide
JP6167911B2 (en) * 2014-01-16 2017-07-26 株式会社村田製作所 Catalyst and reforming method carried out using the same
DE102014011213A1 (en) 2014-07-29 2016-02-04 Linde Aktiengesellschaft Process for synthesis gas production
AR105312A1 (en) * 2014-10-24 2017-09-27 Basf Se SYNTHESIS PROCESS OF ALUMINATES AT HIGH TEMPERATURE THROUGH FLAME SPRAYING PIRÓLISIS
KR20180030633A (en) * 2015-07-09 2018-03-23 우미코레 아게 운트 코 카게 NH3-SCR activity, ammonia oxidation activity, and adsorption capacity for volatile vanadium and tungsten compounds
US10577243B2 (en) * 2015-11-18 2020-03-03 Exxonmobil Research And Engineering Company Reforming catalyst
CN108262046A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 Doped hexaaluminate oxide catalyst, preparation method and application thereof
WO2018219992A1 (en) 2017-06-02 2018-12-06 Basf Se Method for carbon dioxide hydrogenation in the presence of a nickel- and magnesium-spinel-containing catalyst
EP3574994A1 (en) 2018-05-30 2019-12-04 Basf Se Method for producing catalyst monoliths for the reforming of hydrocarbons
EP3917666B1 (en) 2019-01-31 2024-08-07 Basf Se A molding comprising a mixed oxide comprising oxygen, lanthanum, aluminum, and cobalt
CN109939683B (en) * 2019-04-09 2022-03-04 江苏新沃催化剂有限公司 Ternary composite oxide type catalyst for catalytic combustion of VOCs and preparation method thereof
US20230095488A1 (en) 2020-01-31 2023-03-30 Basf Se A process for preparing a molding, a molding and use thereof as methane reforming catalyst
US20230311108A1 (en) 2020-07-29 2023-10-05 Basf Se Solid shaped body and use of the solid shaped body
KR20230043860A (en) 2020-07-29 2023-03-31 바스프 에스이 Solid shaped body and use of the solid shaped body
EP4355687A1 (en) 2021-06-15 2024-04-24 Linde GmbH Method for activating a catalyst
JP2024522689A (en) 2021-06-15 2024-06-21 ビーエーエスエフ ソシエタス・ヨーロピア Method for preparing synthesis gas
JP2024546870A (en) 2021-12-15 2024-12-26 ビーエーエスエフ ソシエタス・ヨーロピア Combined NH3 reforming as a co-feed stream for high pressure NH3 reforming and hydrocarbon/CO2 reforming
JP2025520863A (en) 2022-07-01 2025-07-03 ビーエーエスエフ ソシエタス・ヨーロピア Cobalt-based catalysts for the conversion of hydrocarbons to synthesis gas.
WO2024003347A1 (en) 2022-07-01 2024-01-04 Basf Se Cobalt- and strontium-based catalyst for the conversion of hydrocarbons to synthesis gas
EP4600205A4 (en) * 2022-10-06 2026-01-14 Lg Chemical Ltd CARBON DIOXIDE REFORMATION PROCESS

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US20070111884A1 (en) * 2005-11-14 2007-05-17 Laiyuan Chen Catalyst support, supported catalyst, and methods of making and using the same
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JP2010180096A (en) * 2009-02-05 2010-08-19 Nagoya Institute Of Technology Ceramic porous material and method for producing the same
CN101927160A (en) * 2009-06-26 2010-12-29 中国科学院大连化学物理研究所 A kind of catalyst and its preparation and application

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Publication number Publication date
RU2014136535A (en) 2016-04-10
CN104080530A (en) 2014-10-01
CA2864063A1 (en) 2013-08-15
KR20140126366A (en) 2014-10-30
EP2812111B1 (en) 2025-09-03
DK2812111T3 (en) 2025-11-24
JP6238909B2 (en) 2017-11-29
RU2631497C2 (en) 2017-09-25
WO2013118078A1 (en) 2013-08-15
ZA201406561B (en) 2016-08-31
EP2812111A4 (en) 2015-11-18
JP2015511209A (en) 2015-04-16
EP2812111A1 (en) 2014-12-17
CN104080530B (en) 2018-08-07

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