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WO2009064170A2 - Catalyseur à base de cu-zn-al additionné de palladium pour la production d'hydrogène à partie de méthanol - Google Patents

Catalyseur à base de cu-zn-al additionné de palladium pour la production d'hydrogène à partie de méthanol Download PDF

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Publication number
WO2009064170A2
WO2009064170A2 PCT/MY2009/000006 MY2009000006W WO2009064170A2 WO 2009064170 A2 WO2009064170 A2 WO 2009064170A2 MY 2009000006 W MY2009000006 W MY 2009000006W WO 2009064170 A2 WO2009064170 A2 WO 2009064170A2
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WO
WIPO (PCT)
Prior art keywords
catalyst
methanol
palladium
copper
hydrogen
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Application number
PCT/MY2009/000006
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English (en)
Other versions
WO2009064170A3 (fr
Inventor
Zahira Yaakob
Wan Ramli Wan Daud
Lorna Jeffery Minggu
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Universiti Kebangsaan Malaysia
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Application filed by Universiti Kebangsaan Malaysia filed Critical Universiti Kebangsaan Malaysia
Publication of WO2009064170A2 publication Critical patent/WO2009064170A2/fr
Publication of WO2009064170A3 publication Critical patent/WO2009064170A3/fr

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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
    • 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
    • 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
    • B01J23/8953—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 zinc, cadmium or mercury
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/72—Copper
    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based 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
    • 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
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • 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 catalyst for the hydrogen production from methanol by autothermal steam reforming reaction.
  • this invention relates to a catalyst of copper(Cu)-zinc(Zn)-aluminium(Al) promoted with palladium (Pd) which effectively catalyzes the reforming of methanol to hydrogen to be coupled with Proton Exchange Membrane Fuel Cell (PEMFC).
  • PEMFC Proton Exchange Membrane Fuel Cell
  • hydrogen gas can be produced from methanol by three types of processes, namely steam reforming (SRM), partial oxidation (POX) and autothermal reforming (ATR).
  • SRM steam reforming
  • POX partial oxidation
  • ATR autothermal reforming
  • SRM of methanol is the most common and well-established technology.
  • SRM methanol is reacted with steam to produce hydrogen gas and carbon dioxide with trace amount of carbon monoxide.
  • SRM is a catalytic reaction where the presence of catalyst plays a significant role in the rate and efficiency of the reaction.
  • SRM is widely used in the hydrogen production method since it produces high hydrogen yield as 3 moles of hydrogen gas produced per mole of methanol converted.
  • There are some inventions disclosed in the prior arts pertaining the development of a catalyst for the SRM reaction and a method of producing the catalyst thereof.
  • the catalyst invented is capable of providing sufficient catalytic activity and durability.
  • the catalyst is characterized by comprising copper and zinc, and palladium and/or platinum.
  • the invention also relates to a method of producing hydrogen by using this invented catalyst.
  • Another steam reforming process of methanol to hydrogen gas is described in PCT publication No. WO2004083116.
  • This invention relates to a method for the production of hydrogen by a steam reforming process wherein a catalyst is used.
  • the catalyst comprises Cu in the form of copper oxide and Zr in the form of zirconia. This catalyst is prepared by a templating method.
  • This invention relates to a catalyst comprising copper, zinc, aluminium and zirconium in combination.
  • the method of producing this Cu-Zn-AL-Zr oxide catalyst includes reacting an aqueous sodium hydroxide solution and aqueous sodium carbonate solution with a mixture of aqueous solutions of Cu, Zn, Al, and Zr, producing a precipitate by co-precipitation, preparing a catalyst precursor of Cu-Zn-Al-Zr layered double hydroxide, and calcining this precursor to obtain the catalyst.
  • the invention also relates to a method of producing hydrogen gas by using this oxide catalyst.
  • U. S. Patent No. US2006111457 to Industrial Technology Research Institute of Taiwan also relates to a process for the production of a hydrogen-rich reformate gas by methanol autothermal reforming reaction.
  • This prior art provides a catalyst comprising a platinum deposited on a carrier containing mixed oxide of cerium and zirconium. This catalyst is capable of catalyzing a feed of methanol, water vapour and air to form a hydrogen-rich reformate gas by an autothermal reforming reaction.
  • the primary object of the present invention is to develop a catalyst that composed of palladium, copper and zinc as a metal component supported on alumina which is used for catalyzing the autothermal steam reforming reaction of hydrogen production from methanol.
  • Another object of the present invention is to provide a catalyst of palladium, copper and zinc supported on alumina which is capable of catalyzing autothermal steam reforming reaction of hydrogen production from methanol at low temperature and low pressure.
  • Still another object of the present invention is to provide a composition of a catalyst containing palladium, copper, zinc and alumina for the autothermal steam reforming reaction, in which this catalyst can help in the production of the highest yield of hydrogen and the lowest selectivity to carbon monoxide.
  • Further object of the present invention is to prepare a catalyst which has high surface area and uniform distribution of active species on the surface which are proportional to the increase of catalytic activity.
  • At least one of the preceding objects is met, in whole or in part, by the present invention, in which one of the embodiments of the present invention describes a catalyst for autothermal steam reforming of methanol comprising copper, zinc, palladium or any combination thereof as a metal component supported on alumina.
  • Another embodiment of the present invention is a method for preparing a catalyst comprising copper, zinc, palladium or any combination thereof which is supported on alumina by incipient wetness impregnation process.
  • Still another embodiment of the present invention is a method for producing hydrogen, comprising the step of converting methanol to hydrogen gas by an autothermal steam reforming process in the presence of both oxygen and steam using a catalyst comprising copper, zinc, palladium or any combination thereof as a metal component supported on alumina.
  • the present invention relates to a catalyst for the hydrogen production from methanol by autothermal steam reforming reaction.
  • this invention relates to a catalyst of copper(Cu)-zinc(Zn)-aluminium(Al) promoted with palladium (Pd) which effectively catalyzes the reforming of methanol to hydrogen to be coupled with Proton Exchange Membrane Fuel Cell (PEMFC).
  • PEMFC Proton Exchange Membrane Fuel Cell
  • the present invention discloses a catalyst for autothermal steam reforming of methanol comprising copper, zinc, palladium or any combination thereof as a metal component supported on alumina.
  • the conventional Cu-Zn-Al catalyst is promoted with various concentrations of palladium and supported on alumina.
  • the catalyst is a combination of metals which can be palladium (Pd), copper (Cu), zinc (Zn) or any combination thereof. In the present invention, it is preferably to use the combination of Pd-Cu-Zn. These metals are impregnated and supported on gamma alumina ( ⁇ -A ⁇ Os).
  • the metal component which is the Pd, Cu and Zn are used in different standard values for the preparation of the catalyst.
  • the amount of metal component which includes copper, zinc and palladium in the catalyst is preferably to be 1% to 5% by weight of the catalyst, respectively.
  • the maximum active metal loading on the support is predetermined at 5%. Therefore, a statistical mixture experimental design of Pd-Cu-Zn- Alumina is applied in the present invention. It is based on the response surface method of the design of experiment, whereby the relationship of the factors (the different types of composition of the three metals in the catalyst) and response (efficiency in the catalytic capability of the catalyst) in a process is represented by mathematical equation which is used to model the blending surface. A standard simplex centroid design is used for determining the amount of different metals added into the mixture.
  • the amount of a mixture of copper, zinc and palladium in the catalyst is preferably to be 5% by weight of the catalyst.
  • all three metals, copper, zinc and palladium are added in a percentage of 1.67% by weight of the catalyst. This optimum weight percentage of these three active metals is able to give high activity since high surface area on the support is impregnated by low active material content of the metals.
  • the amount of different metals added into the mixture is determined by the statistical mixture experimental design which aims to find the effect of the different composition in the mixture to the yield and hydrogen and selectivity of carbon dioxide.
  • Gamma-alumina is an enormously important material in catalysis. It is commonly used as a catalyst in hydrocarbon conversion or as a support for automotive and industrial catalysts as in the present invention.
  • Alumina has negligible catalytic activity in the production of hydrogen from methanol. It acts as the support for the impregnation of the copper, zinc and palladium.
  • the amount of alumina in the catalyst is at least 95% by weight of the catalyst.
  • the gamma alumina employed in the present invention has a surface area of 228m 2 /g and its average particle size is approximately 100 micron.
  • the palladium employed in the present invention is preferably Pd(NOs) 2.2EkO
  • the suitable source of Cu is Cu(NO 3 ) 2.3H 2 O
  • the suitable source of Zn is Zn(NOs) 2 -OH 2 O.
  • the catalyst produced is active at low temperature and low pressure for methanol reforming which is favourable when the hydrogen is coupled to PEMFC for automotive application.
  • the catalyst also has high surface area and uniform distribution of active species on the surface which are proportional to the increase of its catalytic activity.
  • Another embodiment of the present invention is a method to prepare a catalyst comprising copper, zinc, palladium or any combination thereof which is supported on alumina by incipient wetness impregnation process.
  • the Pd-Cu-Zn-Y-Al 2 O 3 is prepared by a 2-step process. Initially, the pure Cu and Zn powder are dissolved in an aqueous or organic solvent respectively to form Cu and Zn precursor solution. It is then followed by a co-impregnation process of ⁇ - Al 2 O 3 with the mixture of Cu and Zn precursor solution which is dried and calcined. Consequently, Pd precursor solution is added to the Cu-Zn- ⁇ -Al 2 O 3 by sequential- impregnation. The resulting catalyst is dried at approximately 60°C to 67°C with occasional stirring for one hour and then kept at 110 0 C overnight. The dried catalyst is calcined in nitrogen flow at 500 0 C for 3 hours to decompose the nitrate so as to obtain a pure Pd-Cu-Zn- ⁇ -Al2 ⁇ 3 catalyst.
  • This impregnation method is capable of provide a catalyst which requires less active metal loading to achieve the same catalytic activity and more resistant to sintering.
  • the preparation by co-precipitation method also offers well dispersed active metals throughout the support of alumina.
  • Still another embodiment of the present invention is a method for producing hydrogen, comprising the step of converting methanol to hydrogen gas by an autothermal steam reforming process in the presence of both oxygen and steam using a catalyst comprising copper, zinc, palladium or any combination thereof which is supported on alumina.
  • this autothermal steam reforming reaction is capable of producing hydrogen gas at moderately low temperature which is preferably in a range of 180 0 C to 280 0 C and low pressure of 1 bar to 2 bar.
  • the method for producing hydrogen from methanol as described by the preferred embodiment is a high efficient autothermal reaction where it provides maximum yield of hydrogen and yet consumes minimum level of energy. Accordingly, the maximum yield of hydrogen gas can be 77%.
  • the carbon dioxide selectivity is approximately 1.2% to 73%.
  • Autothermal steam reforming (ATR) reaction as described in the preferred embodiment of the present invention is a combination of the endothermic steam reforming (SRM) reaction and the exothermic partial oxidation (POX) reaction.
  • SRM endothermic steam reforming
  • POX exothermic partial oxidation
  • the catalyst offered a viable way to harness hydrogen from methanol to be used as an energy source for the future especially when methanol is derived from renewable sources such as biomass.
  • the catalyst embodied by the present invention is also applicable for crude oil processing, hydrotreating naphtha, synthesis of methanol from syngas or petrochemicals industry.

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

Abstract

La présente invention concerne un catalyseur pour le reformage auto-thermique par vapeur de méthanol comportant du cuivre, du zinc, du palladium ou toute combinaison de ceux-ci sous forme d'un constituant métallique avec un support d'alumine.
PCT/MY2009/000006 2007-11-16 2009-01-02 Catalyseur à base de cu-zn-al additionné de palladium pour la production d'hydrogène à partie de méthanol WO2009064170A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20072030 2007-11-16
MYPI20072030 MY151052A (en) 2007-11-16 2007-11-16 Cu-zn-al catalyst promoted with palladium for hydrogen production from methanol

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WO2009064170A2 true WO2009064170A2 (fr) 2009-05-22
WO2009064170A3 WO2009064170A3 (fr) 2009-10-22

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452964A (zh) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 一种双功能催化剂及其制备方法与应用
CN115518654A (zh) * 2022-09-30 2022-12-27 四川蜀泰化工科技有限公司 一种高效率、高选择、高稳定的甲醇重整制氢催化剂及其制备工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020039965A1 (en) * 2000-07-18 2002-04-04 Konosuke Hagihara Catalyst for steam reforming of methanol and method for producing hydrogen therewith
US20050158236A1 (en) * 2004-01-21 2005-07-21 Min-Hon Rei Process and reactor module for quick start hydrogen production
US20070020161A1 (en) * 2005-07-22 2007-01-25 Cho Eun-Suk Catalyst for reformer used in fuel cell system, reformer, and fuel cell system comprising same
WO2007105696A1 (fr) * 2006-03-14 2007-09-20 Mitsubishi Gas Chemical Company, Inc. Generateur d'hydrogene et procede de fabrication d'hydrogene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020039965A1 (en) * 2000-07-18 2002-04-04 Konosuke Hagihara Catalyst for steam reforming of methanol and method for producing hydrogen therewith
US20050158236A1 (en) * 2004-01-21 2005-07-21 Min-Hon Rei Process and reactor module for quick start hydrogen production
US20070020161A1 (en) * 2005-07-22 2007-01-25 Cho Eun-Suk Catalyst for reformer used in fuel cell system, reformer, and fuel cell system comprising same
WO2007105696A1 (fr) * 2006-03-14 2007-09-20 Mitsubishi Gas Chemical Company, Inc. Generateur d'hydrogene et procede de fabrication d'hydrogene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452964A (zh) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 一种双功能催化剂及其制备方法与应用
CN114452964B (zh) * 2020-10-21 2024-05-10 中国石油化工股份有限公司 一种双功能催化剂及其制备方法与应用
CN115518654A (zh) * 2022-09-30 2022-12-27 四川蜀泰化工科技有限公司 一种高效率、高选择、高稳定的甲醇重整制氢催化剂及其制备工艺
CN115518654B (zh) * 2022-09-30 2023-07-25 四川蜀泰化工科技有限公司 一种甲醇重整制氢催化剂及其制备工艺

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MY151052A (en) 2014-03-31
WO2009064170A3 (fr) 2009-10-22

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