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WO2004103556A1 - Catalyseurs a oxydes mixtes contenant du manganese et du cobalt destines a l'oxydation de co - Google Patents

Catalyseurs a oxydes mixtes contenant du manganese et du cobalt destines a l'oxydation de co Download PDF

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Publication number
WO2004103556A1
WO2004103556A1 PCT/EP2004/005503 EP2004005503W WO2004103556A1 WO 2004103556 A1 WO2004103556 A1 WO 2004103556A1 EP 2004005503 W EP2004005503 W EP 2004005503W WO 2004103556 A1 WO2004103556 A1 WO 2004103556A1
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Prior art keywords
catalyst
oxides
catalyst according
oxidation
mixed oxide
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German (de)
English (en)
Inventor
Wilhelm Maier
Jens Saalfrank
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Universitaet des Saarlandes
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Universitaet des Saarlandes
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D9/00—Composition of chemical substances for use in breathing apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • 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
    • B01J23/8986—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 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—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
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to mixed oxide catalysts for the oxidation of carbon monoxide containing at least two of the elements Cu, Co, Mn and Ni, processes for their preparation, processes for the oxidation of carbon monoxide in the presence of such catalysts and the use of the catalysts according to the invention in fuel cells, in breathing apparatus or in gas purification.
  • Mixed oxide catalysts for the oxidation of carbon monoxide (CO) are particularly suitable for applications in the field of respiratory protection, low-temperature fuel cells (PEM) and exhaust gas purification.
  • This aspect plays a major role, especially when using methanol as an energy source for non-stationary membrane fuel cells (e.g. in motor vehicles).
  • methanol is generated "on board” by methanol steam reforming. Small amounts (approx. 1%) of CO are produced which poison the anode of the fuel cell. For this reason, catalysts are required which selectively remove the CO in an H 2 - Oxidize the atmosphere to CO 2 without simultaneously consuming H 2 .
  • Hopkalite (“CuMn 2 O”) is currently still used in respiratory masks for the oxidative removal of CO from contaminated breathing air (SH Taylor et al., Applied Catalysis A: General 166 (1998) 143; M. Katz, Advances Catalysis 5 (1953) 177).
  • K. Omata et al., Applied Catalysis A: General 146 (1996) 255 The good activity and selectivity of Pt / aluminum with and without promoters has been known for a long time and is still the subject of research (E. Gulari et al., Applied Catalysis B: Environmental 37 (2002) 17; R. Farrauto et al. , Catalysis Today 62 (2000) 249).
  • Japanese patent JP2001149781 provides the use of Fe, Co and Cu in a Pt-containing catalyst for the selective CO oxidation in an H 2 -containing gas at low temperatures.
  • this object is achieved by mixed oxide catalysts for the oxidation of carbon monoxide containing at least two of the elements Cu, Co, Mn and Ni, the catalyst consisting of 50-99.5 mol% of mixed oxides of these elements or of mixtures of the oxides of the elements, mixed oxides based on Cu and Co are excluded.
  • Such catalysts have higher activities at lower temperatures than conventional catalysts. It has surprisingly been found that mixed oxide catalysts which contain at least two elements from the group Co, Mn, Cu and Ni oxidize CO with high selectivity and activity even at low temperatures.
  • the catalyst preferably consists of 60-98 mol% of mixed oxides of at least two of the elements Cu, Co, Mn and Ni, particularly preferably 70-95 mol%.
  • the catalysts according to the invention can also contain more than two of the elements Cu, Co, Mn and Ni.
  • Another metal can, for example, contain up to 2 mol%, preferably up to 3 mol%.
  • the present invention relates to a catalyst, the catalyst containing> 0% and ⁇ 40% oxides of Mn and> 50% oxides of Cu. It is further preferred that the catalyst consists of> 0% and ⁇ 40% oxides of Mn and> 50% of oxides of Cu, in particular> 10% and ⁇ 40% of oxides of Mn and> 60% of oxides of Cu.
  • the present invention relates to a catalyst, the catalyst containing> 50% oxides of Co or Ni and> 0% and ⁇ 49% oxides of Cu or Mn.
  • a particularly preferred catalyst consists of> 50% of the oxides of Co or Ni and> 0% and ⁇ 49% of oxides of Cu or Mn, for example> 60% of the oxides of Co or Ni and> 10% and ⁇ 40% from oxides of Cu or Mn.
  • Another catalyst according to the invention contains a manganese / cobalt mixed oxide, the Co / Mn ratio being> 4.
  • the catalyst preferably consists of manganese / cobalt mixed oxide, the Co / Mn ratio being> 4, preferably> 8.
  • the catalyst contains a nickel / manganese mixed oxide and the Ni / Mn ratio is between 1.5 and 4. It is preferred that the catalyst consists of nickel / manganese mixed oxide and the Ni / Mn ratio is between 1.5 and 4.
  • the present invention relates to a catalyst, the catalyst consisting of mixed copper oxide with Co, Mn or Ni, the Cu content being less than 45%, in particular ⁇ 40%, for example ⁇ 35%.
  • the invention also relates to a catalyst which is present as a mixed oxide of> 40% Ni,> 0 and ⁇ 50% Mn,> 0 and ⁇ 5% Ag and> 0 and ⁇ 5 Co, preferably> 60% Ni,> 0 and ⁇ 40% Mn,> 0 and ⁇ 5% Ag and> 0 and ⁇ 5 Co.
  • the most active catalysts have a cobalt / manganese ratio of greater than 4, in particular greater than 8, particularly preferably greater than 10.
  • catalysts are furthermore preferred according to the invention which contain at least one further component selected from noble metals or alkali metals or a component from the group of the elements aluminum, titanium, silicon, zirconium or mixtures of all.
  • Aluminum is particularly preferred.
  • the catalyst preferably contains at least 0.5 mol%, particularly preferably at least 1.0 mol%, in particular 5.0 mol% of the further component.
  • the noble metals are preferably Pt, Pd, Ir, Ru, Ag or Rh, Pt being preferred.
  • the alkali metals are preferably the oxides or carbonates of K, Cs or Rb.
  • the catalyst fulfills one of the following conditions:
  • Such catalysts have particularly high activities and selectivities.
  • the oxide mixture has proven to be particularly active proved.
  • This catalyst has a high stability against air humidity at room temperature. At 25 ° C and a relative humidity of ⁇ 85%, about 90% of the carbon monoxide present is oxidized after a reaction time of 60 minutes.
  • the catalysts of the invention can be used both in pure form and also applied to suitable support materials and moldings customary in heterogeneous catalysis, i.e. that the catalyst is present as a full catalyst or supported catalyst. Depending on the application, it may be necessary to adjust the pore size and porosity of the prior art catalysts by varying the production conditions.
  • the catalyst can be crystalline or amorphous; the catalyst is preferably amorphous.
  • the present invention also relates to a production process for the mixed oxide catalysts according to the invention.
  • the catalyst can be produced by precipitation, impregnation, sol-gel methods or powder synthesis.
  • the present invention relates to a production process for a mixed oxide catalyst according to the invention comprising a sol-gel process and subsequent calcining.
  • the catalysts according to the invention have high activities and selectivities even at relatively low temperatures.
  • the present invention therefore also relates to a process for the oxidation of CO in the presence of the mixed oxide catalysts according to the invention, which is carried out in a temperature range from -20 ° C. to + 200 ° C.
  • the process is preferably carried out at temperatures from 0 to 120 ° C., in particular at 5 to 80 ° C., particularly preferably at 20 ° C. to 30 ° C., for example at 25 ° C.
  • the method according to the invention can also be operated with moist or dry air, in particular with moist air.
  • the catalyst according to the invention converts CO selectively both in oxidizing and in reducing medium.
  • the process according to the invention is therefore suitable both for the selective oxidation of CO in reducing, hydrogen-rich gas mixtures and for the oxidation of CO in oxidizing, oxygen-rich gas mixtures.
  • the gas mixture used originates from a methanol reforming process.
  • Gas mixtures derived from a methane or hydrocarbon reforming process can also be used.
  • it is preferred that the gas mixture comes from the ambient air.
  • the process according to the invention can be carried out using a mixed oxide catalyst alone.
  • the catalyst is used together with H 2 O adsorbers, such as zeolites or superabsorbers.
  • the catalysts are suitable for removing CO from air or other gases, e.g. Hydrogen, in the temperature range from -10 to 200 ° C.
  • the invention provides an application for the selective CO oxidation in the presence of hydrogen (fuel cells) and for the CO oxidation in air (breathing apparatus, exhaust gas purification) at low temperatures.
  • the catalysts of the invention are particularly suitable for use in fuel cells (selective removal of CO in a hydrogen-rich environment), in respiratory masks and respiratory protective devices (fire and mining, civil protection, occupational safety), in exhaust air purification from chemical production processes, in the exhaust air from internal combustion engines, e.g. in the cold start phase, in exhaust air purification in combustion power plants and domestic fire systems, in indoor air purification in closed units (submarine, aircraft, space technology, test laboratories), in CO 2 laser devices
  • the catalysts of the invention show high selectivity and activity even at low temperatures. This is particularly advantageous for use in fuel cells and breathing apparatus that are operated at temperatures around 20 ° C.
  • the present invention therefore also relates to the use of the mixed oxide catalysts according to the invention in fuel cells, in breathing apparatus and in that of exhaust air purification.
  • Example 1 CO oxidation in dry air
  • the investigations to determine the activity of the mixed oxide catalysts for CO oxidation were carried out in a flow tube reactor.
  • the gases (CO, synthetic air, H 2 ) were metered using mass flow controllers and the gas composition before and after the catalyst was determined using suitable gas sensors.
  • the gas composition of individual gas samples was checked using GC analysis.
  • the reactor consisted of a glass reactor tube, which was surrounded by a heater for adjusting the measuring temperature.
  • the catalyst was on a piece of glass wool in the reactor tube.
  • Example 2 The tests for CO oxidation in moist air were carried out using the same experimental setup as described in Example 1.
  • the reaction gas (1 vol.% CO in synthetic air, 50 mL / min total volume flow) was saturated with water at room temperature by passing it through a water-filled one Washer bottle was directed.
  • the measurement was carried out with 200 mg (100-200 ⁇ m sieve fraction) of the mixed oxide catalyst according to Example 8 at 25 ° C. and a relative atmospheric humidity of ⁇ 85%. Under these reaction conditions, the mixed oxide catalyst Pto, 5Al ⁇ Mn6, Co 91; 8 O x showed a CO conversion of 90% after 60 minutes.
  • Example 3 CO oxidation in a dry hydrogen atmosphere
  • the tests for CO oxidation in a dry hydrogen atmosphere were carried out using the same experimental setup as described in Example 1.
  • the reaction gas consisted of 1 vol.% CO and 5 vol.% Synthetic air in H 2 and was used with a total volume flow of 50 ml / min.
  • the measurements were carried out with 200 mg (100
  • Example 4 CO oxidation in a humid hydrogen atmosphere
  • the investigations on CO oxidation in a moist hydrogen atmosphere were carried out using the same experimental setup as described in Example 1.
  • the reaction gas was saturated with water at room temperature by passing it through a wash bottle filled with water.
  • the reaction gas was accordingly composed of 1% by volume of CO, 5% by volume of synthetic air and approximately 2.3% by volume of H 2 O in H 2 .
  • the total volume flow was 50 mL / min.
  • the measurements were carried out with 100 mg (100-200 ⁇ m sieve fraction) of the catalyst according to Example 8 at 60, 80, 100 and 120 ° C.
  • Example 6 Comparative example
  • the commercially available CO oxidation catalyst hopkalite (“CuMn 2 O 4 ”) was measured in dry air and in moist air at 25 ° C.
  • the experimental set-up as described in Example 1 and Example 2 was used. The same was used After 60 minutes, Hopkalit showed a CO conversion of 66% in dry air. In moist air, the catalyst was completely deactivated after a measuring time of 60 minutes.
  • the experimental set-up as described in Example 5 was used to investigate the activity at low temperatures Under the same reaction conditions, the CO conversion of hopkalite was 10% at 5 ° C. after 30 minutes.
  • the catalyst CuO-CeO 2 (Matralis et al., Catalysis Today 75 (2002) 157) was investigated as a comparative example for CO oxidation in a dry and moist hydrogen atmosphere.
  • the experimental set-up as described in Example 3 and Example 4 was used under the same reaction conditions.
  • CuO-CeO 2 showed a CO conversion of 73% at 80 ° C after 30 minutes with a selectivity of 100%.
  • the catalyst CuO-CeO 2 was poisoned by the H 2 O and no conversion of CO was found.
  • Example 13 Preparation of the catalyst Ag ⁇ , 5Cu 23; 5 Co 5 ⁇ x

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Abstract

L'invention concerne des catalyseurs à oxydes mixtes destinés à l'oxydation de monoxyde de carbone, contenant au moins deux des éléments suivants : Cu ; Co ; Mn et Ni. Selon l'invention, le catalyseur est composé de 50 à 99,5 % en mol d'oxydes mixtes de ces éléments, ou de mélanges des oxydes de ces éléments, à l'exception d'oxydes mixtes à base de Cu et de Co. L'invention concerne également des procédés de fabrication desdits catalyseurs, des procédés d'oxydation de monoxyde de carbone en présence de tels catalyseurs, et l'utilisation desdits catalyseurs dans des piles à combustibles, des appareils de protection respiratoire ou dans la décontamination de l'air rejeté.
PCT/EP2004/005503 2003-05-22 2004-05-21 Catalyseurs a oxydes mixtes contenant du manganese et du cobalt destines a l'oxydation de co Ceased WO2004103556A1 (fr)

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DE10323539 2003-05-22
DE10323539.6 2003-05-22

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009021850A1 (fr) * 2007-08-10 2009-02-19 Süd-Chemie AG PROCÉDÉ POUR ÉLIMINER CO, H2 ET/OU CH4 DES EFFLUENTS GAZEUX DE L'ANODE D'UNE PILE À COMBUSTIBLE AVEC DES CATALYSEURS OXYDES MIXTES COMPRENANT Cu, Mn ET ÉVENTUELLEMENT AU MOINS UN MÉTAL DES TERRES RARES
CN101071880B (zh) * 2007-05-21 2010-05-26 哈尔滨工业大学 被动式自呼吸直接甲醇燃料电池的串联电池组
WO2012000883A1 (fr) * 2010-06-30 2012-01-05 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'oléfines à partir d'un gaz de synthèse, en utilisant un catalyseur contenant du cobalt et du manganèse
EP2404656A3 (fr) * 2010-07-08 2012-12-12 Air Products And Chemicals, Inc. Traitement de gaz combustible à partir d'un procédé de combustion de gaz combustible
US9327238B2 (en) 2010-11-18 2016-05-03 Clariant Corporation Method for removing CO, H2 and CH4 from an anode waste gas of a fuel cell and catalyst system useful for removing these gases
WO2017001679A1 (fr) * 2015-07-02 2017-01-05 Technische Universität Dresden Procédé de production de nanoparticules d'oxyde métallique mixte rendues hydrophobes et utilisation de celles-ci pour la catalyse hétérogène
CN111135835A (zh) * 2019-12-17 2020-05-12 安徽元琛环保科技股份有限公司 一种一氧化碳催化氧化催化剂及其制备方法与应用

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071880B (zh) * 2007-05-21 2010-05-26 哈尔滨工业大学 被动式自呼吸直接甲醇燃料电池的串联电池组
WO2009021850A1 (fr) * 2007-08-10 2009-02-19 Süd-Chemie AG PROCÉDÉ POUR ÉLIMINER CO, H2 ET/OU CH4 DES EFFLUENTS GAZEUX DE L'ANODE D'UNE PILE À COMBUSTIBLE AVEC DES CATALYSEURS OXYDES MIXTES COMPRENANT Cu, Mn ET ÉVENTUELLEMENT AU MOINS UN MÉTAL DES TERRES RARES
KR101410856B1 (ko) 2007-08-10 2014-06-24 클라리안트 프로두크테 (도이칠란트) 게엠베하 Ｃｕ, Ｍｎ 및 선택적으로 적어도 하나의 희토류 원소를 포함하는 혼합 산화물 촉매로 연료 전지의 양극 폐가스로부터 ＣＯ, Ｈ2 및/또는 ＣＨ4를 제거하는 방법
WO2012000883A1 (fr) * 2010-06-30 2012-01-05 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'oléfines à partir d'un gaz de synthèse, en utilisant un catalyseur contenant du cobalt et du manganèse
US8569388B2 (en) 2010-06-30 2013-10-29 Shell Oil Company Process for preparing olefins from synthesis gas using a cobalt and manganese containing catalyst
EP2404656A3 (fr) * 2010-07-08 2012-12-12 Air Products And Chemicals, Inc. Traitement de gaz combustible à partir d'un procédé de combustion de gaz combustible
US9327238B2 (en) 2010-11-18 2016-05-03 Clariant Corporation Method for removing CO, H2 and CH4 from an anode waste gas of a fuel cell and catalyst system useful for removing these gases
WO2017001679A1 (fr) * 2015-07-02 2017-01-05 Technische Universität Dresden Procédé de production de nanoparticules d'oxyde métallique mixte rendues hydrophobes et utilisation de celles-ci pour la catalyse hétérogène
US10874891B2 (en) 2015-07-02 2020-12-29 Technische Universität Dresden Method for producing hydrophobized mixed metal oxide nanoparticles and use thereof for heterogeneous catalysis
CN111135835A (zh) * 2019-12-17 2020-05-12 安徽元琛环保科技股份有限公司 一种一氧化碳催化氧化催化剂及其制备方法与应用

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