EP1843844A1 - Composition a activite catalytique destinee a la methanisation selective de monoxyde de carbone et procede de fabrication de cette composition - Google Patents

Composition a activite catalytique destinee a la methanisation selective de monoxyde de carbone et procede de fabrication de cette composition

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Publication number
EP1843844A1
EP1843844A1 EP06707761A EP06707761A EP1843844A1 EP 1843844 A1 EP1843844 A1 EP 1843844A1 EP 06707761 A EP06707761 A EP 06707761A EP 06707761 A EP06707761 A EP 06707761A EP 1843844 A1 EP1843844 A1 EP 1843844A1
Authority
EP
European Patent Office
Prior art keywords
catalytically active
methanation
catalyst
carbon monoxide
active composition
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06707761A
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German (de)
English (en)
Inventor
Christian Kuhrs
Markus HÖLZLE
Till Gerlach
Michael Hesse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1843844A1 publication Critical patent/EP1843844A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • 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
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
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    • 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
    • C01B3/586—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 a methanation reaction
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    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • 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
    • B01J23/847—Vanadium, niobium or tantalum or polonium
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C01B2203/0445—Selective methanation
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • 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
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    • 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
    • C01B2203/1052—Nickel or cobalt catalysts
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    • 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
    • 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

  • Catalytically active composition for the selective methanation of carbon monoxide and process for its preparation
  • the invention relates to a catalytic composition and a process for the selective methanation of carbon monoxide, in particular for use in fuel cell systems.
  • Low-temperature fuel cells can only be operated with hydrogen or hydrogen-rich gases of a defined quality.
  • the CO concentration depends on the energy source used and the reforming process used. The removal of higher CO concentrations is possible with the shift process with further formation of hydrogen. However, depending on the method design, a residual concentration of CO remains, generally in the range from 0.5 to 1.5% by volume. When using Cu catalysts, for example, CO removal can be made possible down to 3,000 ppm. The CO content in the hydrogen-rich gas must be further reduced as much as possible in order to avoid poisoning of the anode catalyst.
  • the CO methanation (hydrogenation of carbon monoxide to methane) is carried out according to the reaction equation:
  • the particular challenge for selective CO methanation is that preferably CO should be hydrogenated and not CO 2 , as this would consume more hydrogen.
  • the CO methanation is opposite the CO 2 methanation preferred. It is known that below a limit of 200 to 300 ppm CO concentration in the fuel gas does not use the CO 2 methanation.
  • the CO concentration in the fuel gas is about 10,000 ppm, which is 50 times higher than the specified limit.
  • the CO 2 content is about 15 to 25 vol .-% an order of magnitude above the CO content. Accordingly, a CO-selective catalyst is indispensable.
  • EP-A-1174486 combines a methanation step with a selective oxidation unit for the purpose of lower oxygen consumption and lower CO 2 methanation rate.
  • WO 97/43207 describes the combination of a first stage for selective oxidation with a subsequent methanation stage. With this combination, both processes can be operated under optimal conditions.
  • JP-A-2004097859 describes catalysts for the removal of CO in hydrogen-containing gas streams by reaction with H 2 .
  • Catalysts mentioned are inorganic see support on which one or more metals selected from the group Ru, Ni and Co, are applied.
  • Support materials are TiO 2 , ZrO 2 , Al 2 O 3 and zeolites.
  • JP-A-2002068707 relates to a process for removing CO from hydrogen-containing gas by selective methanation of CO using a catalyst having a Ru component and an alkali metal and / or alkaline earth metal on a refractory inorganic oxide support.
  • coal as a catalyst carrier has not previously been described for the methanation of carbon monoxide.
  • the object of the invention was therefore to provide a catalyst for the selective CO methanation, which receives its selectivity and activity in a wide temperature range.
  • a catalytically active composition which contains as the active component ruthenium, rhodium, nickel or cobalt and a support material based on coal and is optionally doped.
  • the invention thus provides a catalytically active composition for the selective methanation of carbon monoxide, which is characterized in that it contains as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt, and a support material based on coal.
  • Objects of the invention are also the use of this catalytically active composition for the selective methanation of carbon monoxide and for use in fuel cell applications.
  • the catalytically active composition contains as active component at least one element selected from the group consisting of Ru, Rh, Ni and Co, preferably Ru.
  • Coal such as activated carbon acid activated activated carbon, graphite or pyrolytic carbon is used as support material according to the invention, preferably activated carbon moldings are used.
  • the loading of the carrier material with the active component is preferably 0.1 to 20 wt .-%, particularly preferably 1 to 10 wt .-%.
  • the active component and / or the carrier material can be doped.
  • iron, niobium, manganese, molybdenum and zirconium are suitable as doping elements. Preference is given to doping with iron.
  • the doping elements are used in an amount of preferably 0.1 to 20 wt .-%, particularly preferably 1 to 10 wt .-%.
  • the preparation of the catalyst according to the invention is carried out in a customary manner, for example by bringing the active components, preferably in the form of their salts / hydrates, into solution and then applying them to the carbon carrier in a suitable manner, for example by impregnation. Thereafter, the catalyst is dried, possibly calcined, optionally reduced and passivated if necessary.
  • the CO carried in a temperature range of preferably 100 to 300 0 C, the selective methanation.
  • the catalytically active composition is therefore particularly suitable for use in hydrogen production for fuel cell applications.
  • the selectivity is the quotient of the amount of CO converted and the amount of methane produced (in% by volume).
  • the indication "ve” means that CO 2 is fully preserved, and sales are based on CO.
  • Activated carbon strands with a diameter of 3 mm and a length of about 2 to 5 mm were introduced and soaked in drops of the prepared solution. Carrier and impregnation solution were well mixed throughout the impregnation process.
  • the catalyst was dried in a rotary kiln at 90 ° C with 150 l / h of nitrogen for six hours. Immediately after the drying process the catalyst was reduced in the rotary kiln with a flow of 15 l / h of hydrogen and 60 l / h of nitrogen. The oven was heated to 500 ° C within two hours and then held at 500 0 C for three hours. Thereafter, the catalyst was cooled to room temperature under nitrogen. Gradually more and less air and less nitrogen were fed in over 2 hours, whereby the catalyst was passivated. The temperature of the catalyst was not more than 15 ° C above room temperature. For the activity test described under 2 a), the catalyst was comminuted to 1-2 mm chippings.
  • the catalyst mixture consisted of 10 g of catalyst (as 1 to 2 mm grit), which in the case of the catalyst according to Example 1 corresponds to a volume of about 21 ml, with about 10 ml steatite spheres with a diameter of
  • the catalyst was initially at 90 l / h of nitrogen and 10 l / h of hydrogen at
  • the gas composition chosen for the experiment is typical of the exit of the cryogenic post stage after reforming of methane: 33 vol.% H 2 ; 28% by volume of N 2 ; 25% by volume H 2 O; 13% by volume of CO 2 ; 0.5% by volume of CO; 0.5% by volume of CH 4 .
  • a load of 5 lg Ka t "1 h " 1 was chosen.
  • the catalyst according to Example 3 a) was first activated in the reactor with a hydrogen / nitrogen gas mixture and then at a load of 2.5 l g ⁇ at "1 h " 1 in a gas stream with 33 vol .-% H 2 ; 25% by volume H 2 O; 28.25 vol.% N 2 ; 13% by volume of CO 2 ; 0.25% by volume of CO; 0.5 vol .-% CH 4 operated.
  • the temperature was varied between 120 and 220 0 C in 10 K increments.
  • the measurement results for selectivity, conversion and final CO concentration are shown in the following table.
  • the very wide temperature window in which the catalyst can be operated becomes clear.
  • the catalyst of the invention according to Example 1 was at the load of 2.5 lg cat "1 h " 1 and the following gas composition (33 vol .-% H 2 ; 25 vol .-% H 2 O; 28.25 Vol.% N 2 , 13% by volume of CO 2 , 0.25% by volume of CO, 0.5% by volume of CH 4 ) were operated for a period of 1000 hours at a temperature of 175 ° C. Over the runtime, a CO concentration of ⁇ 50 ppm was realized. Over time, CO 2 was unaffected by the reaction. The concentration of 50 ppm CO is the limit for the operation of fuel cells based on polymer electrolyte membranes.
  • Example 5 emphasizes the long-term stability of the catalyst.
  • the inventive catalyst according to Example 1 was operated in series with a commercially usable catalyst for the low-temperature conversion.
  • the catalyst for the selective methanization underwent a load of 2.5 l g ⁇ at "1 h " 1 .
  • Example 5 a) shows the values for the operation of a TTK catalyst at 210 ° C.
  • 5 b) for the operation of a TTK catalyst at 220 ° C.
  • the inventive catalyst according to Example 1 was subjected to a series of atmospheric changes under operating conditions.
  • a gas composition 1 (2.5 l g ⁇ at "1 h " 1 , 33% by volume H 2 , 25% by volume H 2 O, 28.25% by volume N 2 , 13% by volume of CO 2 , 0.25% by volume of CO, 0.5% by volume of CH 4 ) were converted to air after brief purging with nitrogen. After renewed nitrogen purge was switched back to the original gas composition 1.

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  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne une composition à activité catalytique destinée à la méthanisation sélective de monoxyde de carbone, caractérisée en ce qu'elle contient, en tant que composant actif, au moins un élément choisi dans le groupe composé de ruthénium, rhodium, nickel et cobalt, et un matériau support à base de carbone. L'invention concerne également l'utilisation de cette composition à activité catalytique pour la méthanisation sélective de monoxyde de carbone, et son utilisation dans la production d'hydrogène dans des applications de cellules électrochimiques.
EP06707761A 2005-01-24 2006-01-19 Composition a activite catalytique destinee a la methanisation selective de monoxyde de carbone et procede de fabrication de cette composition Withdrawn EP1843844A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005003311A DE102005003311A1 (de) 2005-01-24 2005-01-24 Katalytisch aktive Zusammensetzung zur selektiven Methanisierung von Kohlenmonoxid und Verfahren zu deren Herstellung
PCT/EP2006/050312 WO2006077236A1 (fr) 2005-01-24 2006-01-19 Composition a activite catalytique destinee a la methanisation selective de monoxyde de carbone et procede de fabrication de cette composition

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EP1843844A1 true EP1843844A1 (fr) 2007-10-17

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US (1) US7560496B2 (fr)
EP (1) EP1843844A1 (fr)
JP (1) JP2008528250A (fr)
CA (1) CA2595466A1 (fr)
DE (1) DE102005003311A1 (fr)
WO (1) WO2006077236A1 (fr)

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CN101631613B (zh) * 2007-03-13 2013-01-30 乌米科雷股份两合公司 作为一氧化碳甲烷化的催化剂的掺杂金属的氧化镍
EP2336083A1 (fr) 2009-12-17 2011-06-22 Topsøe Fuel Cell A/S Générateur de gaz et procédés pour la conversion de carburant en gaz désoxygéné et/ou gaz enrichi en hydrogène
JP5662044B2 (ja) * 2010-03-31 2015-01-28 大阪瓦斯株式会社 触媒の活性化の程度を判定する方法
DE102011085165A1 (de) 2011-10-25 2013-04-25 Wacker Chemie Ag Verfahren zur Herstellung von Vinylacetat
JP5889613B2 (ja) * 2011-11-25 2016-03-22 国立大学法人群馬大学 金属担持用担体、金属担持触媒、メタネーション反応装置及びこれらに関する方法
DE102011121930A1 (de) * 2011-12-22 2013-06-27 Solarfuel Gmbh Methanisierungsreaktor
EP3072589A1 (fr) 2015-03-26 2016-09-28 Basf Se Catalyseur et procédé de méthanisation sélective de monoxyde de carbone
CN108136386B (zh) * 2015-10-05 2024-01-30 巴斯夫欧洲公司 制备钌/铁/碳载体催化剂的方法

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Also Published As

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US20080139676A1 (en) 2008-06-12
US7560496B2 (en) 2009-07-14
WO2006077236A1 (fr) 2006-07-27
CA2595466A1 (fr) 2006-07-27
DE102005003311A1 (de) 2006-07-27
JP2008528250A (ja) 2008-07-31

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