WO2004004895A1 - Procede de preparation d'un catalyseur d'oxydation preferentielle et processus d'oxydation preferentielle - Google Patents

Procede de preparation d'un catalyseur d'oxydation preferentielle et processus d'oxydation preferentielle Download PDF

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Publication number
WO2004004895A1
WO2004004895A1 PCT/EP2003/006931 EP0306931W WO2004004895A1 WO 2004004895 A1 WO2004004895 A1 WO 2004004895A1 EP 0306931 W EP0306931 W EP 0306931W WO 2004004895 A1 WO2004004895 A1 WO 2004004895A1
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WIPO (PCT)
Prior art keywords
catalyst
hydrogen
carbon monoxide
gas stream
rich gas
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PCT/EP2003/006931
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English (en)
Inventor
Esmond Newson
Truong Thanh-Binh
Original Assignee
Paul Scherrer Institut
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
Priority claimed from EP02015061A external-priority patent/EP1391240A1/fr
Application filed by Paul Scherrer Institut filed Critical Paul Scherrer Institut
Priority to AU2003249906A priority Critical patent/AU2003249906A1/en
Publication of WO2004004895A1 publication Critical patent/WO2004004895A1/fr

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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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

Definitions

  • the invention relates to a method for preparing a catalyst for preferential oxidation to remove carbon monoxide from a hydrogen-rich gas, a process for preferential oxidation to remove carbon monoxide from a hydrogen-rich gas and and a method for operating a fuel cell system.
  • Hydrogen is currently used mainly in industry, in activities such as the manufacture of fertilizers, petroleum processing, methanol synthesis, annealing of metals and producing electronic materials. In the foreseeable future, the emergence of fuel cell technology will extend the use of hydrogen to domestic and vehicle applications.
  • PEM proton exchange membrane
  • the first automobile manufacturers have successfully launched prototype vehicles comprising PEM fuel cell stacks not larger than a conventional combustion engine. These stacks offer a permanent power of about 40 to 50 kWe while operating with neat hydrogen. Advanced experiences from powering submarines with PEM fuel cells show for the PEM fuel cell system technology a rapid development whereby the choice of fuel for a passenger vehicle did not so far keep pace.
  • CO removal by adsorption By adsorption, reduction or oxidation.
  • Adsorption processes typically require unacceptably large volumes of adsorbent.
  • catalytic materials including noble metals (Pt, Pd, Rh and Ru) and base metals, such as Co/Cu, Ni/Co/Fe, Ag, Cr, Fe and Mn, were evaluated in a laboratory reactor feedstream containing CO, H 2 , in order to identify alternate catalysts which are more effective than currently used Pt/Al 2 0 3 in selectively oxidizing CO in the presence of excess hydrogen.
  • Ru/Al 2 0 3 and Rh/Al 2 0 3 are among the most active catalysts for CO oxidation, achieving nearly complete CO conversion at temperatures as low as 100°C as compared to approx. 200°C required for currently used Pt/Al 2 0 3 .
  • the Ru/Al 2 0 3 and Rh/Al 2 0 3 catalysts were found to be exceptionally selective for CO oxidation, making it possible to purify the fuel cell feedstream with a minimum loss of the energy content associated with the hydrogen content .
  • this aim with respect to the method for preparing a catalyst for preferential oxidation to remove carbon monoxide from a hydrogen-rich gas stream, comprising: a) forming an impregnated support material by impregnating a metal oxide or a mixture of metal oxides with a soluble rare earth metal compound or with a soluble mixture of rare earth metal compounds; b) drying the impregnated support material; and c) forming the catalyst by dispersing a precious metal or a mixture of precious metals on the impregnated support material .
  • metal oxide is alumina.
  • possible materials as refractory support material can be at least one of the group containing titania, zirconia and silica. With respect to a suitable rare earth metal compound excellent carbon monoxide conversion rates result from using a cerium-salt as a rare earth compound.
  • cerium hydroxide a cerium halide, a cerium oxyhalide, cerium nitrate, cerium ammonium nitrate cerium carbonite, cerium acetate, cerium oxalate, a cerium alkoxide such as cerium methoxide, cerium ethoxide, cerium propoxide, cerium isopropoxide or cerium butoxide, or the like.
  • cerium alkoxide may be preferably employed.
  • a cerium compound also a compound or a mixture of compounds from at least one rare earth metal selected from the group containing Praseodym, Neodym and Gadolinium.
  • the dispersion of the precious metal or the mixture of precious metals can be reached by impregnating the impregnated support material with a soluble precious metal compound or with a soluble mixture of precious metal compounds .
  • rhodium or ruthenium is rhodium or ruthenium.
  • a raw material of rhodium there may be mentioned, for example, a rhodium halide such as rhodium chloride or the like; a halogenated rhodinate such as sodium chlororhodinate, ammoniumchlororhodinate or the like; a halogenated rhodinic acid such as chlororhodinic acid or the like; a rhodiumhydroxide such as rhodium (III) hydroxide, rhodium (IV) hydroxide or the like; rhodium nitrate; rhodium oxide; or an organic rhodium compound such as rhodium carbonyl or the like.
  • a rhodium halide such as rhodium chloride or the like
  • a halogenated rhodinate such as sodium chlororhodinate,
  • the raw material of ruthenium there may be mentioned, for example, a ruthenium halide such as ruthenium iodide, ruthenium chloride or the like; a halogenated ruthenate such as ammonium chlororuthenate or the like; a halogenated ruthenic acid such as chloro-ruthenic acid or the like; a ruthenate such as potassium ruthenate or the like; or an organic ruthenium compound such as ruthenium carbonyl or the like.
  • ruthenium trichloride or ruthenium nitrosylnitrate is preferably employed.
  • these raw materials for the precious metal ingredient of the catalyst may be employed singly or in combination of two or more.
  • the amount of precious metal is 0.01 to 10, preferably 0.05 to 5 weight per cent of the total weight of the catalyst which is also advantageous with respect to the manufacturing costs.
  • the process comprises: contacting the hydrogen-rich gas stream with a catalyst, manufactured according the method given above, under the condition of elevated temperature and pressure as compared with standard condition (20°C, 1 bar) .
  • a suitable hydrogen-rich gas stream can be attained by passing a feed stream comprising a hydrocarbon or an oxygenate to a fuel processor comprising an integrated steam reforming and water gas shift conversion zone; said hydrogen- rich gas stream then comprises hydrogen, carbon monoxide, carbon dioxide, oxygen and water vapor.
  • a feed stream comprising a hydrocarbon or an oxygenate
  • a fuel processor comprising an integrated steam reforming and water gas shift conversion zone
  • said hydrogen- rich gas stream then comprises hydrogen, carbon monoxide, carbon dioxide, oxygen and water vapor.
  • the supply of oxygen has to be controlled to find both a maximum for oxidizing carbon monoxide and to cut down the supply for the undesired hydrogen oxidation.
  • the concentration of oxygen in the hydrogen-rich gas stream should be maintained between 1 to 10 times (lambda), preferably 2.5 to 5.0 times (lambda), of the stoichiometric requirement for the maximum conversion of CO to CO- and the minimum conversion of H,.
  • the figure shows that essentially 100% CO conversion is attained for 2.5 ⁇ lambda ⁇ 4.0 while maintaining not more than 5-10% of the undesired H 2 conversion.
  • the data given in figure 1 have been measured with a catalyst and the micro reactor data condition as set out below in the description of some illustrative examples.
  • the concentration of water vapor offered to the catalyst has a significant impact on the performance of the catalytic process as shown in the two step reaction mechanism below, [1], [2], the water deriving from (undesirable) hydrogen oxidation and from the vapour partial pressure of condensed water in the condenser (@10C) of the reformer product gases.
  • the oxygen in the auxiliary air reoxidises the Ru(0) which is required again to be reduced to allow the carbon monoxide to be oxidized to the desired carbon dioxide.
  • Qualitative confirmation of the above catalyst surface mechanism is provided by pH measurements (4-5) of condensed water from prox product gases exiting the prox reactor. On titration of the water condensate with a silver nitrate solution, a black precipitate of silver chloride was regularly observed.
  • X-ray photoelectron spectroscopy (XPS) analyses of fresh and deactivated catalysts also shows chloride present in fresh catalysts, hence RuC12 in [1], and depletion of chloride (ex alumina) in the deactivated catalysts after 1700 hours onstream.Full details of these phenomena are to be found in a recent publication by E.Newson et al . , Studies in Surface
  • a) the temperature is between 60 and 250°C, preferably between 80 and 150°C; and/or b) the pressure is between 1 to 10 bar, preferably between 2 to 5 bar; and/or c) the gas hourly space velocity (litres of feed gas at standard condition/hour/litre reactor volume) is between 20,000 to 200,000 per hour, preferably between 50,000 and 150, 000 per hour.
  • the invention comprises a process for preferential oxidation for removing carbon monoxide from a hydrogen-rich gas stream being performed under the conditions as described above.
  • a feed stream comprising a hydrocarbon or an oxygenate to a fuel processor comprising a catalyst forming an integrated steam reformation and water gas shift conversion zone to produce a fuel stream, i.e. a hydrogen- rich gas, at a catalyst temperature lower than 700°C followed by passing the fuel stream over a catalyst for preferential oxidation to produce a purified fuel gas at least approximately free from carbon monoxide.
  • a fuel stream i.e. a hydrogen- rich gas
  • a catalyst temperature lower than 700°C followed by passing the fuel stream over a catalyst for preferential oxidation to produce a purified fuel gas at least approximately free from carbon monoxide.
  • An excellent efficiency for the removal of the carbon monoxide can be achieved by a fuel stream containing about 50 to 50.000 ppm carbon monoxide.
  • a high longterm reliability, i.e. a longterm activity of the anode of a PEM fuel cell, is reached by supplying a purified fuel gas containing less than 10 ppm carbon monoxide.
  • Example 1 CO preferential oxidation (PROX) catalyst
  • a batch of catalyst with a nominal composition of 5%Ru/5%CeO/Al 2 0_ (based on the proportion of the precursors) was prepared by first impregnating the crushed alumina support material with an aqueous Ce-salt solution to form a slurry; drying the slurry by the rotavap method and calcining the product in an airflow oven to provide a cerium doped support (CeO/Al 2 0 3 ) .
  • this cerium doped alumina support material was impregnated with an aqueous Ruthenium salt solution to form a slurry followed by drying the slurry by the rotavap method and afterwards calcining the product in an airflow oven to give the nominal compositions 5%Ru/5%CeO/Al 2 0 3 (hereinafter referred to as PSI Ex.l).
  • Cerium doped support 1 gram of crushed alumina support was impregnated with stirring for three hours with 4.0 ml of cerium(iv) ammonium nitrate (12.78 mg Ce/ml) . The resulting slurry was transferred to a rotavap apparatus and dried at 85°C and 100 mbar pressure. Drying was completed in a drying oven overnight at 120°C and 100 mbar vacuum. Calcination with an airflow of 100 ml/min at 500°C for three hours completed the preparation of the cerium doped support (CeO/Al 2 0 3 ) .
  • PROX catalyst 3.6 ml ruthenium nitrosylnitrate (14 mg Ru/ml) was added to the cerium doped support with stirring for three hours. The slurry was transferred to a rotavap apparatus and dried at 85°C and 100 mbar pressure. Drying was completed in a drying oven overnight at 120°C. Calcination with an airflow of 100 ml/min at 550°C for three hours completed the preparation of the PROX catalyst with a nominal composition of 5%Ru/5%Ce/Al 2 0 3 .
  • Catalyst activation takes place in the reactor by heating up in N 2 to 200°C for outgassing, Va hour hold, reduction in H 2 between 250 and 450°C, two hour hold, cool to 200°C in H 2 , purge with N 2 to 120°C.
  • the support material may be in all other reasonable form suitable for fixed bed reactor applications, such as spheres, extrudates, cylinders, tablets, rings and half-rings. It could be alternatively also in the form of monoliths or other structured support packings, such as ceramic honeycomb bodies, stacks of juxtaposed metallic plate-type catalysts having the catalytic material coated on the surfaces of the metallic plates, for fixed bed applications.
  • the CO is removed from reformate gas to levels below 10 ppm implying conversions of 99.9%, allowing its use for PEM fuel cell operation without deactivating the fuel cell anode catalyst.
  • the concomitant H 2 conversion should be far below 10% to maintain the overall efficiency of the reformer-PROX connection and facilitate heat management in the reactor.
  • Ruthenium on a cerium doped alumina support is approximately 75 to 142 times more active than the prior art catalyst UOP and Toyota resp. Additionally, the stability of the PSI catalyst was demonstrated by continuous operation at various conditions for 1200 hours.
  • the surprising feature of the PSI catalyst is that the increased activity is not due to an additional metal promoter such as lithium (Toyota) or to an significantly higher content of a noble metal but the promotion of the support alumina with cerium oxide, presumably increasing its oxygen adsorption and dissociation properties. In detail, this higher activity is presumably caused by the nano-distribution of the cerium on the alumina support.
  • the catalyst prepared under impregnation with the aqueous cerium-salt solution does not show any peaks for ceria in an -XRD analysis implying that both the ceria and the noble metal content are dispersed that far that grains over 50 Angstrom have not been built and as a consequence peaks for ceria and the noble metal could not be observed.
  • Cat.Tod The second catalyst referred to as "Cat.Tod.” is the catalyst which is disclosed in the article “Selective catalytic oxidation of CO in H 2 : fuel cell applications” from Olga Korothikh and Robert Farrauto, published in Catalysis Today 62 (2000) 249 to 254.
  • the PSI Ex.l catalyst with a 5 wt . % ruthenium content on a cerium doped alumina support in comparison with the Appl.Cat.B. catalyst and the Cat. Tod. catalyst is 10 times and 32 times, resp., more active than these catalysts taken from the recently published scientific literature.
  • Table 3 shows the prox data with hydrocarbon derived reformates from both gaseous and liquid pox feeds. The data shows that with the C. to C 3 feeds the high selectivity for CO conversion is maintained with low H 2 conversions what is considered to be most desirable.
  • the nano-distribution of the cerium compound on the alumina lead to the significant increase of the catalytic activity of the catalyst.
  • this nano-distribution of a rare earth metal compound not only serves as a stabilizing compound for the metal oxide support compound -but contributes in a non-negligible manner already to the catalytic activity of the catalyst.
  • the use of other noble metal compounds such as platinum, iridium but also compounds from tungsten, molybdenum can be considered in a reasonable manner.
  • the cerium might be changed with or supplemented with another or a group of other rare earth metal compounds, such as the oxides of praseodym, neodym and gadolinium.

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

Abstract

L'invention concerne un procédé permettant de préparer un catalyseur d'oxydation préférentielle pour éliminer le monoxyde de carbone contenu dans un flux gazeux riche en hydrogène. Ledit procédé comprend les étapes suivantes : former un matériau support imprégné, par imprégnation d'un oxyde de métal ou d'un mélange d'oxydes de métal avec un composé de métal des terres rares ou avec un mélange soluble de composés de métaux des terres rares ; sécher le matériau support imprégné, et former le catalyseur par dispersion d'un métal précieux ou d'un mélange de métaux précieux sur le matériau support imprégné. L'invention concerne en outre un processus d'oxydation préférentielle pour enlever le monoxyde de carbone contenu dans un flux gazeux riche en hydrogène, ledit processus comprenant : mettre en contact le flux gazeux riche en hydrogène avec un catalyseur, produit selon le procédé mentionné ci-dessus, dans des conditions de température et de pression élevées, comparativement aux conditions standard (20 °C, 1 bar). L'invention concerne par ailleurs un procédé d'exploitation d'un système de cellule à combustible, comprenant un processus d'oxydation préférentielle pour éliminer le monoxyde de carbone contenu dans un flux gazeux riche en oxygène, se déroulant dans les conditions mentionnées ci-dessus. Ce processus s'effectue de manière successive après un processus combinant le reformage à la vapeur et la réaction de conversion d'un flux gazeux contenant à l'origine un hydrocarbone ou un oxygénate.
PCT/EP2003/006931 2002-07-05 2003-06-30 Procede de preparation d'un catalyseur d'oxydation preferentielle et processus d'oxydation preferentielle WO2004004895A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003249906A AU2003249906A1 (en) 2002-07-05 2003-06-30 Method for preparing a catalyst for preferential oxidation and a process thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02015061.1 2002-07-05
EP02015061A EP1391240A1 (fr) 2002-06-03 2002-07-05 Methode de préparation d'un catalyseur pour l'oxidation preféréntielle du monoxide de carbone dans un gaz riche en hydrogène, procédé pour l'oxidation preféréntielle du monoxide de carbone dans un gaz rich en hydrogène, et une methode pour le fonctionnement d'une pile à combustible

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861591A (zh) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 选择氧化脱除co的负载型纳米金催化剂及其制备和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367166A (en) * 1980-07-17 1983-01-04 Kabushiki Kaisha Toyota Chuo Kenkyusho Steam reforming catalyst and a method of preparing the same
EP0503653A1 (fr) * 1991-03-12 1992-09-16 Nippon Oil Company, Limited Catalyseur pour le reformage à la vapeur à haute température d'hydrocarbures
WO1998035908A1 (fr) * 1997-02-14 1998-08-20 Shell Internationale Research Maatschappij B.V. Oxydation catalytique partielle d'hydrocarbures
DE10053989A1 (de) * 1999-11-04 2001-05-23 N E Chemcat Corp Katalysator für die selektive Oxidation von Kohlenmonoxid in wasserstoffhaltigen Gasen, Verfahren zur Entfernung von Kohlenmonoxid und Festpolymer-Elektrolyt-Brennstoffzellensystem unter Verwendung des Katalysators
EP1138383A1 (fr) * 1998-11-26 2001-10-04 Idemitsu Kosan Company Limited Catalyseur d'oxydation de monoxyde de carbone, procede de preparation d'un catalyseur d'oxydation de monoxyde de carbone, et procede de production d'un gaz contenant de l'hydrogene
US6299995B1 (en) * 2000-05-31 2001-10-09 Uop Llc Process for carbon monoxide preferential oxidation for use with fuel cells

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4367166A (en) * 1980-07-17 1983-01-04 Kabushiki Kaisha Toyota Chuo Kenkyusho Steam reforming catalyst and a method of preparing the same
EP0503653A1 (fr) * 1991-03-12 1992-09-16 Nippon Oil Company, Limited Catalyseur pour le reformage à la vapeur à haute température d'hydrocarbures
WO1998035908A1 (fr) * 1997-02-14 1998-08-20 Shell Internationale Research Maatschappij B.V. Oxydation catalytique partielle d'hydrocarbures
EP1138383A1 (fr) * 1998-11-26 2001-10-04 Idemitsu Kosan Company Limited Catalyseur d'oxydation de monoxyde de carbone, procede de preparation d'un catalyseur d'oxydation de monoxyde de carbone, et procede de production d'un gaz contenant de l'hydrogene
DE10053989A1 (de) * 1999-11-04 2001-05-23 N E Chemcat Corp Katalysator für die selektive Oxidation von Kohlenmonoxid in wasserstoffhaltigen Gasen, Verfahren zur Entfernung von Kohlenmonoxid und Festpolymer-Elektrolyt-Brennstoffzellensystem unter Verwendung des Katalysators
US6299995B1 (en) * 2000-05-31 2001-10-09 Uop Llc Process for carbon monoxide preferential oxidation for use with fuel cells

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861591A (zh) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 选择氧化脱除co的负载型纳米金催化剂及其制备和应用
CN103861591B (zh) * 2012-12-18 2016-01-27 中国科学院大连化学物理研究所 选择氧化脱除co的负载型纳米金催化剂及其制备和应用

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