EP1843844A1 - Catalytically active composition for the selective methanation of carbon monoxide and method for producing said composition - Google Patents
Catalytically active composition for the selective methanation of carbon monoxide and method for producing said compositionInfo
- 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- Withdrawn
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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
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- 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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- B01J37/0201—Impregnation
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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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- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- 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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- 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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Abstract
The invention relates to a catalytically active composition for the selective methanation of carbon monoxide. Said composition is characterised in that it contains as the active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt and a carbon-based support. The invention also relates to the use of said catalytically active composition for the selective methanation of carbon monoxide and to the use of the composition for generating hydrogen in fuel-cell applications.
Description
Katalytisch aktive Zusammensetzung zur selektiven Methanisierung von Kohlen- monoxid und Verfahren zu deren HerstellungCatalytically active composition for the selective methanation of carbon monoxide and process for its preparation
Beschreibungdescription
Die Erfindung betrifft eine katalytische Zusammensetzung und ein Verfahren zur selektiven Methanisierung von Kohlenmonoxid, insbesondere für die Verwendung in Brennstoffzellensystemen.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.
Niedertemperatur-Brennstoffzellen können nur mit Wasserstoff oder wasserstoffreichen Gasen einer definierten Qualität betrieben werden. Die CO-Konzentration hängt vom eingesetzten Energieträger und vom verwendeten Reformierungsverfahren ab. Die Entfernung von höheren CO-Konzentrationen ist mit dem Shiftprozess unter weiterer Bildung von Wasserstoff möglich. Es verbleibt aber in Abhängigkeit von der Verfah- rensauslegung eine Restkonzentration an CO, in der Regel im Bereich von 0,5 bis 1 ,5 Vol.-%. Bei Verwendung von Cu-Katalysatoren kann beispielsweise eine CO- Entfemung bis hinunter zu 3.000 ppm ermöglicht werden. Der CO-Gehalt im wasserstoffreichen Gas muss so weit wie möglich weiter reduziert werden, um eine Vergiftung des Anodenkatalysators zu vermeiden.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.
Die Reduzierung des enthaltenen CO aus dem Gasstrom bis unter die erforderlichen Grenzwerte erfolgt üblicherweise in einer Feinreinigungsstufe. Dabei ist heute die selektive Oxidation die gängige CO-Entfernungsmethode. Die selektive Oxidation weist einen hohen Entwicklungsstand auf, besitzt aber neben dem Nachteil einer nur mäßi- gen Selektivität die Notwendigkeit einer exakt dosierten Luftzufuhr, woraus ein hoher mess- und regelungstechnischer Aufwand resultiert. Dazu kommt über die Zumischung des Oxidationsmittels Sauerstoff zum Gas eine sicherheitstechnische Problematik. Die Entfernung des CO durch Reaktion mit H2 (Methanisierung) hat gegenüber der selektiven CO-Oxidation durch ihre verfahrenstechnisch anspruchslose Realisierung erhebli- che Vorteile.The reduction of CO contained in the gas stream to below the required limits is usually carried out in a fine cleaning stage. Today, selective oxidation is the common CO removal method. The selective oxidation has a high level of development, but in addition to the disadvantage of only moderate selectivity has the need for a precisely dosed air supply, resulting in a high measurement and control engineering effort. Added to this is the addition of the oxidant oxygen to the gas a safety problem. The removal of CO by reaction with H 2 (methanation) has considerable advantages over selective CO oxidation due to its unproblematic implementation.
Die CO-Methanisierung (Hydrierung von Kohlenstoffmonoxid zu Methan) erfolgt nach der Reaktionsgleichung:The CO methanation (hydrogenation of carbon monoxide to methane) is carried out according to the reaction equation:
CO + 3H2 → CH4 + H2O ΔH = -206,2 kJ/molCO + 3H 2 → CH 4 + H 2 O ΔH = -206.2 kJ / mol
Als Konkurrenzreaktion läuft die Umwandlung von CO2 zu Methan ab:As a competing reaction, the conversion of CO 2 to methane takes place:
CO2 + 4H2 → CH4 + 2H2O ΔH = -164,9 kJ/molCO 2 + 4H 2 → CH 4 + 2H 2 O ΔH = -164.9 kJ / mol
Die besondere Herausforderung für die selektive CO-Methanisierung liegt darin, dass bevorzugt CO hydriert werden soll und nicht CO2, da dies weiteren Wasserstoff verbrauchen würde. Nach der Thermodynamik wird die CO-Methanisierung gegenüber
der CO2-Methanisierung bevorzugt. Es ist bekannt, dass unterhalb eines Grenzwertes von 200 bis 300 ppm CO-Konzentration im Brenngas die CO2-Methanisierung nicht einsetzt. Die CO-Konzentration liegt im Brenngas bei ca. 10.000 ppm, also um den Faktor 50 höher als die angegebene Grenze. Der CO2-Gehalt liegt mit ca. 15 bis 25 Vol.-% eine Größenordnung über dem CO-Gehalt. Dementsprechend ist ein CO- selektiver Katalysator unabdingbar.The particular challenge for selective CO methanation is that preferably CO should be hydrogenated and not CO 2 , as this would consume more hydrogen. According to thermodynamics, 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.
Die selektive Methan isierung von CO ist seit langem bekannt. Zunächst wurde CO am Ni-Katalysator methanisiert, wobei CO2 jedoch zuvor ausgewaschen werden musste. 1968 wurde ein Ruthen iumkatalysator zur selektiven CO-Methanisierung von Baker et al. beansprucht (US-A-3615164), wobei dort ein Ruthenium- oder Rhodiumkatalysator auf einem Aluminiumoxid-Trägermaterial verwendet wird. Ebenso ist in Chemical Abstracts, Band 74, 1971, Nr. 35106u, die selektive Methanisierung von CO in einem Gasgemisch, das Wasserstoff, Kohlendioxid und Kohlenmonoxid enthält, bei Tempera- turen im Bereich zwischen 125 und 3000C unter Verwendung rutheniumhaltiger Katalysatoren beschrieben. In US-A-3663162 von 1972 wird ein Raney-Nickel-Katalysator für diese Reaktion beansprucht.The selective methanization of CO has long been known. First, CO was methanized on the Ni catalyst, but CO 2 had to be previously washed out. In 1968, a ruthenium catalyst for the selective CO methanation of Baker et al. (US Pat. No. 3,615,164), where a ruthenium or rhodium catalyst is used on an alumina support material. Also, in Chemical Abstracts, Volume 74, 1971, no. 35106u, the selective methanation of CO in a gas mixture containing hydrogen, carbon dioxide and carbon monoxide, at temperatures in the range 125-300 0 C using ruthenium catalysts. In US-A-3663162 of 1972, a Raney nickel catalyst is claimed for this reaction.
In EP-A-1174486 wird eine Methan isierungsstufe mit einer Einheit zur selektiven Oxi- dation mit dem Ziel eines geringeren Sauerstoffverbrauches und einer geringeren CO2- Methanisierungsrate kombiniert.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.
In EP-A-0946406 werden zwei Methanisierungsstufen unterschiedlicher Temperaturniveaus zusammengeschaltet. Vorteil soll hier sein, dass bei der Hochtemperaturstufe noch kein oder weniger CO2 methanisiert, aber schon ein großer Teil des Kohlenmon- oxids abgebaut wird. In der sich anschließenden Tieftemperaturmethanisierung erfolgt die Restentfernung von CO.In EP-A-0946406 two methanation stages of different temperature levels are interconnected. The advantage here is that no or less CO 2 is methanized at the high-temperature stage, but even a large part of the carbon monoxide is degraded. In the subsequent low-temperature methanation, the residual removal of CO.
WO 97/43207 beschreibt die Kombination einer ersten Stufe zur selektiven Oxidation mit einer nachfolgenden Methanisierungsstufe. Mit dieser Kombination sollen sich beide Prozesse unter optimalen Bedingungen betreiben lassen.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.
Weitere neuere Anmeldungen, wie beispielsweise EP-A-1246286, in der als letzte Prozessstufe einer Gasreinigung ein Methanisierungsreaktor einer Einheit zur selektiven Oxidation mit der Begründung des einfacheren Aufbaus und der einfacheren Betreib- barkeit bevorzugt wird, beinhalten ebenfalls optimierte Verfahrensstufen, verwenden jedoch auch herkömmliche Katalysatoren, überwiegend auf Ruthenium- oder Nickelbasis.Other recent applications, such as EP-A-1246286, in which a methanation reactor of a selective oxidation unit is preferred as the final process step of gas purification for ease of construction and ease of operation, also include optimized process steps, but also use conventional ones Catalysts predominantly based on ruthenium or nickel.
JP-A-2004097859 beschreibt Katalysatoren zur Entfernung von CO in wasserstoffhalti- gen Gasströmen durch Reaktion mit H2. Als Katalysatoren genannt werden anorgani-
sehe Träger, auf denen ein oder mehrere Metalle, ausgewählt aus der Gruppe Ru, Ni und Co, aufgebracht sind. Trägermaterialien sind TiO2, ZrO2, AI2O3 sowie Zeolithe.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 betrifft ein Verfahren zur Entfernung von CO aus wasserstoffhalti- gern Gas durch selektive Methanisierung des CO unter Verwendung eines Katalysators mit einer Ru-Komponente und einem Alkalimetall und/oder Erdalkalimetall auf einem hitzebeständigen anorganischen Oxidträger.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.
Die Verwendung von Kohle als Katalysatorträger wurde bisher für die Methanisierung von Kohlenmonoxid nicht beschrieben.The use of coal as a catalyst carrier has not previously been described for the methanation of carbon monoxide.
Die Verfahren des Standes der Technik gestatten es nicht, eine ausreichende Senkung des CO-Gehaltes unter Schonung des CO2-Gehaltes zu gewährleisten. Die vorgeschlagenen Katalysatoren arbeiten entweder nicht selektiv genug bzw. wirken nur in einem schmalen Temperaturbereich.The processes of the prior art do not allow to ensure a sufficient reduction in the CO content while sparing the CO 2 content. The proposed catalysts either do not work selectively or act only in a narrow temperature range.
Durch die Exothermie der Reaktion kommt es zu Hot-Spots. Aus diesem Grund muss ein breites Temperaturfenster fahrbar sein. Ebenso ein Problem ist die adiabate Temperaturerhöhung in Monolithen, wenn diese als Katalysatorformkörper eingesetzt wer- den, was in der Praxis der Fall ist.The exothermic reaction leads to hot spots. For this reason, a wide temperature window must be mobile. Another problem is the adiabatic temperature increase in monoliths, when these are used as shaped catalyst bodies, which is the case in practice.
Insbesondere für Brennstoffzellenanwendungen stellen der geforderte CO- Maximalgehalt im eingespeisten wasserstoffreichen Gas und die notwendige hohe Selektivität (Methanisierung von CO, aber nicht von CO2) über ein breites Temperatur- fenster noch ein großes Entwicklungspotential für geeignete deaktivierungsresistente Katalysatoren dar.In particular, for fuel cell applications, the required maximum CO content in the fed hydrogen-rich gas and the necessary high selectivity (methanation of CO, but not of CO 2 ) over a broad temperature window are still a great development potential for suitable deactivation-resistant catalysts.
Die Aufgabe der Erfindung bestand damit in der Bereitstellung eines Katalysators für die selektive CO-Methanisierung, der seine Selektivität und Aktivität in einem breiten Temperaturbereich erhält.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.
Die Aufgabe wurde erfindungsgemäß dadurch gelöst, dass für die selektive Methanisierung von Kohlenmonoxid eine katalytisch aktive Zusammensetzung eingesetzt wird, die als Aktivkomponente Ruthenium, Rhodium, Nickel oder Cobalt und ein Trägermate- rial auf Kohlebasis enthält und gegebenenfalls dotiert ist.The object has been achieved according to the invention in that, for the selective methanation of carbon monoxide, a catalytically active composition is used which contains as the active component ruthenium, rhodium, nickel or cobalt and a support material based on coal and is optionally doped.
Gegenstand der Erfindung ist damit eine katalytisch aktive Zusammensetzung für die selektive Methanisierung von Kohlenmonoxid, die dadurch gekennzeichnet ist, dass sie als Aktivkomponente wenigstens ein Element, ausgewählt aus der Gruppe bestehend aus Ruthenium, Rhodium, Nickel und Cobalt, und ein Trägermaterial auf Kohlebasis enthält.
Gegenstände der Erfindung sind weiterhin die Verwendung dieser katalytisch aktiven Zusammensetzung für die selektive Methanisierung von Kohlenmonoxid sowie für den Einsatz in Brennstoffzellenanwendungen.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.
Es wurde überraschend gefunden, dass ein Ru-, Rh-, Ni- oder Co-haltiger Katalysator auf einem Kohleträger, der gegebenenfalls insbesondere mit Fe dotiert ist, die Methanisierung von CO in einem breiten Temperaturbereich von etwa 100 bis 300°C in einer nahezu konstanten Selektivität über eine lange Zeitspanne gewährleistet. Herkömmliche Katalysatoren zeigen mit zunehmender Temperatur einen deutlichen Selektivitäts- abfall. Durch Anwendung des erfindungsgemäßen Katalysators ist ein deutlich geringerer Regelaufwand erforderlich, da das Temperaturfenster bei der Methanisierung des CO weniger exakt eingehalten werden muss. Darüber hinaus kann ein auch bei hohen Temperaturen gut arbeitender Katalysator direkt der Vorreinigungsstufe (TTK - Tieftemperaturkonvertierung), die bei etwa 220 bis 2800C betrieben wird, nachgeschaltet werden.It has surprisingly been found that a Ru, Rh, Ni or Co-containing catalyst on a carbon support, which is optionally doped with Fe in particular, the methanation of CO in a wide temperature range of about 100 to 300 ° C in a nearly ensures constant selectivity over a long period of time. Conventional catalysts show a significant drop in selectivity with increasing temperature. By applying the catalyst according to the invention a significantly lower control effort is required because the temperature window in the methanation of the CO must be kept less accurate. In addition, a well working catalyst even at high temperatures directly downstream of the pre-purification stage (TTK - low temperature conversion), which is operated at about 220 to 280 0 C, followed.
Die katalytisch aktive Zusammensetzung enthält als Aktivkomponente wenigstens ein Element, ausgewählt aus der Gruppe bestehend aus Ru, Rh, Ni und Co, vorzugsweise Ru.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.
Als Trägermaterial wird erfindungsgemäß Kohle, wie beispielsweise Aktivkohle säureaktivierte Aktivkohle, Graphit oder pyrolytischer Kohlenstoff verwendet, vorzugsweise werden Aktivkohleformkörper eingesetzt.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.
Die Beladung des Trägermaterials mit der Aktivkomponente beträgt vorzugsweise 0,1 bis 20 Gew.-%, besonders bevorzugt 1 bis 10 Gew.-%.The loading of the carrier material with the active component is preferably 0.1 to 20 wt .-%, particularly preferably 1 to 10 wt .-%.
Zur Erhöhung ihrer Aktivität und/oder Selektivität können die Aktivkomponente und/oder das Trägermaterial dotiert werden. Als Dotierelemente eignen sich insbeson- dere Eisen, Niob, Mangan, Molybdän und Zirkonium. Bevorzugt wird mit Eisen dotiert.To increase their activity and / or selectivity, the active component and / or the carrier material can be doped. In particular iron, niobium, manganese, molybdenum and zirconium are suitable as doping elements. Preference is given to doping with iron.
Die Dotierelemente werden in einer Menge von vorzugsweise 0,1 bis 20 Gew.-%, besonders bevorzugt 1 bis 10 Gew.-%, eingesetzt.The doping elements are used in an amount of preferably 0.1 to 20 wt .-%, particularly preferably 1 to 10 wt .-%.
Die Herstellung des erfindungsgemäßen Katalysators erfolgt auf übliche Art und Weise, beispielsweise indem die Aktivkomponenten, vorzugsweise in Form ihrer Salze/Hydrate, in Lösung gebracht und dann in geeigneter Weise, beispielsweise durch Tränken, auf den Kohleträger aufgetragen werden. Danach wird der Katalysator getrocknet, ggf. kalziniert, ggf. reduziert und ggf. passiviert.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.
Es entsteht eine katalytisch aktive Zusammensetzung, die für die selektive Methanisierung von Kohlenmonoxid hervorragend geeignet ist. In Abhängigkeit von den jeweiligen
Reaktionsbedingungen wird dabei die gewünschte deutliche Abreicherung des CO im Gasgemisch erreicht.The result is a catalytically active composition which is outstandingly suitable for the selective methanation of carbon monoxide. Depending on the particular Reaction conditions while the desired significant depletion of CO in the gas mixture is achieved.
Vorteilhafterweise kann damit die selektive Methanisierung des CO in einem Tempera- turbereich von vorzugsweise 100 bis 3000C erfolgen.Advantageously, therefore the CO carried in a temperature range of preferably 100 to 300 0 C, the selective methanation.
Die katalytisch aktive Zusammensetzung eignet sich damit insbesondere für den Einsatz bei der Wasserstofferzeugung für Brennstoffzellenanwendungen.The catalytically active composition is therefore particularly suitable for use in hydrogen production for fuel cell applications.
Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlas- sen.Further embodiments of the present invention can be taken from the claims, the description and the examples. It goes without saying that the features mentioned above and those still to be explained below of the article according to the invention can be used not only in the respectively indicated combination but also in other combinations without departing from the scope of the invention.
Die Erfindung wird anhand der nachfolgenden Ausführungsbeispiele näher erläutert, ohne jedoch hierdurch eine entsprechende Eingrenzung vorzunehmen.The invention will be explained in more detail with reference to the following embodiments, but without thereby making a corresponding limitation.
BeispieleExamples
Zur Auswertung der Ergebnisse der Beispiele wurden die Größen Selektivität und Umsatz herangezogen. Die Selektivität ist der Quotient von umgesetzter Menge CO und der Menge an entstandenem Methan (in Vol.-%). Die Angabe „v.e." steht dafür, dass CO2 vollständig erhalten bleibt. Der Umsatz bezieht sich auf CO.To evaluate the results of the examples, the variables selectivity and conversion were used. 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.
Beispiel 1example 1
Präparation eines Katalysators auf C-Basis mit 5 Gew.-% Ru und 1 Gew.-% Fe, 3 mmPreparation of a C-based catalyst with 5 wt.% Ru and 1 wt.% Fe, 3 mm
Strängestrands
4,4 g Ruthenium(l I l)chlorid-hydrat wurden in 15,0 ml VE-Wasser und 2,4 g Eisen(lll)- chlorid-hydrat in 10,0 ml VE-Wasser gelöst. Die Lösungen wurden zusammengegeben und mit VE-Wasser auf 90 % der Wasseraufnahme des Aktivkohleträgers, die in diesem Fall 0,95 cπrVg betrug, verdünnt (Gesamtvolumen 41 ,0 ml).4.4 g of ruthenium (III) chloride hydrate were dissolved in 15.0 ml of deionized water and 2.4 g of iron (III) chloride hydrate in 10.0 ml of deionised water. The solutions were combined and diluted with deionized water to 90% of the water uptake of the activated charcoal carrier, which in this case was 0.95 cπrVg (total volume 41.0 ml).
Aktivkohlestränge mit einem Durchmesser von 3 mm und einer Länge von ungefähr 2 bis 5 mm wurden vorgelegt und tropfenweise mit der hergestellten Lösung getränkt. Träger und Tränklösung wurden während des gesamten Tränkvorganges gut durchmischt.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.
Anschließend wurde der Katalysator in einem Drehrohrofen bei 90°C mit 150 l/h Stickstoff für sechs Stunden getrocknet. Direkt im Anschluss an den Trocknungsvorgang
wurde der Katalysator im Drehrohrofen mit einem Strom von 15 l/h Wasserstoff und 60 l/h Stickstoff reduziert. Dabei wurde der Ofen innerhalb von zwei Stunden auf 500°C aufgeheizt und dann für drei Stunden bei 5000C gehalten. Danach wurde der Katalysator unter Stickstoff auf Raumtemperatur abgekühlt. Es wurde innerhalb von zwei Stun- den nach und nach immer mehr Luft und weniger Stickstoff zugefahren, wodurch der Katalysator passiviert wurde. Die Temperatur des Katalysators lag dabei nicht mehr als 15°C über Raumtemperatur. Für den unter 2 a) beschriebenen Aktivitätstest wurde der Katalysator zu 1-2 mm Splitt zerkleinert.Subsequently, 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.
Beispiele 2 a) und b)Examples 2 a) and b)
Selektive MethanisierungSelective methanation
2 a) Für den Versuch wurde ein elektrisch beheizter Rohrreaktor mit einem Volumen von 50 ml und einem Durchmesser von 14 mm verwendet.2 a) An electrically heated tubular reactor with a volume of 50 ml and a diameter of 14 mm was used for the experiment.
Zuunterst wurden 4 ml Steatit-Kugeln mit einem Durchmesser von 1 ,8 bis 2,2 mm eingebaut, auf die anschließend die Katalysatormischung gegeben wurde. Die Katalysatormischung bestand aus 10 g Katalysator (als 1 bis 2 mm Splitt), was im Falle des Katalysators gemäß Beispiel 1 einem Volumen von ca. 21 ml entspricht, der mit ca. 10 ml Steatit-Kugeln mit einem Durchmesser vonAt the bottom, 4 ml of steatite spheres with a diameter of 1.8 to 2.2 mm were installed, to which the catalyst mixture was then added. 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
1 ,8 bis 2,2 mm gut durchmischt wurde. Als Vorschüttung dienten 14 ml Steatit- Kugeln mit einem Durchmesser von 1 ,8 bis 2,2 mm, die das Restvolumen des Reaktors füllten.1, 8 to 2.2 mm was well mixed. The feed used was 14 ml of steatite spheres with a diameter of 1.8 to 2.2 mm, which filled the residual volume of the reactor.
Der Katalysator wurde zunächst mit 90 l/h Stickstoff und 10 l/h Wasserstoff beiThe catalyst was initially at 90 l / h of nitrogen and 10 l / h of hydrogen at
230°C eine Stunde lang reduziert. Die für den Versuch gewählte Gaszusammensetzung ist typisch für den Ausgang der Tieftemperatur-Stiftstufe nach der Reformierung von Methan: 33 Vol.-% H2; 28 Vol.-% N2; 25 Vol.-% H2O; 13 Vol.-% CO2; 0,5 Vol.-% CO; 0,5 Vol.-% CH4. Es wurde eine Belastung von 5 l gKat"1 h"1 gewählt.230 ° C for one hour reduced. 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.
Nachdem alle Gase eingestellt und der Reaktor (nach der Reduktion bei 2300C) auf 1500C abgekühlt war, wurde der Versuch gestartet. Alle drei Stunden wurde die Temperatur innerhalb von 10 Minuten um 25°C erhöht, die Maximaltempera- tur betrug 3000C.After all gases had been adjusted and the reactor (after the reduction at 230 ° C.) had cooled to 150 ° C., the test was started. Every three hours the temperature was raised within 10 minutes to 25 ° C, the Maximaltempera- structure was 300 0 C.
2 b) Der unter 2 a) beschriebene Versuch wurde wiederholt, wobei aber ein herkömmlicher Katalysator auf Basis von AI2O3 mit 5 Gew.-% Ru und 1 Gew.-% Fe (als 1 bis 2 mm Splitt) zum Einsatz kam.2 b) The experiment described under 2 a) was repeated, but using a conventional catalyst based on Al 2 O 3 with 5 wt .-% Ru and 1 wt .-% Fe (as 1 to 2 mm grit) was used ,
Es wurden folgende Ergebnisse erzielt: Selektivität (siehe auch Diagramm 1)
Temperatur 0C 5 % Ru + 1 % Fe/C 5 % Ru + 1 % Fe/AI2O3 The following results were achieved: selectivity (see also diagram 1) Temperature 0 C 5% Ru + 1% Fe / C 5% Ru + 1% Fe / Al 2 O 3
240 71 % 9 %240 71% 9%
260 62 % 7 %260 62% 7%
280 44 % 7 %280 44% 7%
300 61 % 6 %300 61% 6%
Umsatz (siehe auch Diagramm 2)Sales (see also diagram 2)
Temperatur 0C 5 % Ru + 1 % Fe/C 5 % Ru + 1 % Fe/AI2O3 Temperature 0 C 5% Ru + 1% Fe / C 5% Ru + 1% Fe / Al 2 O 3
240 95 % 97 %240 95% 97%
260 97 % 98 %260 97% 98%
280 89 % 99 %280 89% 99%
300 90 % 99 %300 90% 99%
Aus Diagramm 2 wird deutlich, dass der Umsatz beider Katalysatoren vergleichbar ist (wenn auch für den herkömmlichen Katalysator auf AI2O3-Basis leicht höher). Diagramm 1 zeigt jedoch, dass bei dem erfindungsgemäßen Katalysator eine deutlich hö- here Selektivität erreicht wird. Zudem ist klar zu erkennen, dass besonders bei niedriger Temperatur der erfindungsgemäße Katalysator sehr gute Selektivitäten bietet.From Diagram 2 it is clear that the conversion of both catalysts is comparable (although slightly higher for the conventional catalyst based on Al 2 O 3 ). However, diagram 1 shows that a significantly higher selectivity is achieved with the catalyst according to the invention. In addition, it can be clearly seen that, especially at low temperature, the catalyst according to the invention offers very good selectivities.
Beispiel 3 a)Example 3 a)
70 g 3 mm Stränge Supersorbon SX 30 (Fa Lurgi) wurden vorgelegt und bei 80°C mit 150 ml HNO3 (konz.) für fünf Stunden aktiviert. Die aktivierte Kohle wurde anschließend gewaschen und bei 1200C getrocknet.70 g of 3 mm extrudates of Supersorbon SX 30 (Fa Lurgi) were initially introduced and activated at 80 ° C. with 150 ml of HNO 3 (conc.) For five hours. The activated carbon was then washed and dried at 120 0 C.
7,3 g Ruthenium(lll)chlorid wurden in Wasser gelöst und mit einer Lösung, 2,4 g Ei- sen(lll)chlorid enthaltend, gemischt, auf 41 ml Wasser verdünnt und langsam zu der aktivierten Kohle gegeben. Der Katalysator wurde bei 900C unter Stickstoff getrocknet, dann in einem Stickstoff-Wasserstoffstrom bei 500°C reduziert. Nach dem Abkühlen wurde das Material bei Raumtemperatur passiviert.7.3 g of ruthenium (III) chloride were dissolved in water and mixed with a solution containing 2.4 g of iron (III) chloride, diluted to 41 ml of water and slowly added to the activated carbon. The catalyst was dried at 90 0 C under nitrogen, then reduced in a nitrogen stream of hydrogen at 500 ° C. After cooling, the material was passivated at room temperature.
Beispiel 3 b)Example 3 b)
Der Katalysator nach Beispiel 3 a) wurde zunächst im Reaktor mit einem Wasserstoff/Stickstoff-Gasgemisch aktiviert und dann bei einer Belastung von 2,5 l gκat "1 h"1 in einem Gasstrom mit 33 Vol.-% H2; 25 Vol.-% H2O; 28,25 Vol.% N2; 13 Vol.-% CO2; 0,25 VoL- % CO; 0,5 Vol.-% CH4 betrieben. Die Temperatur wurde zwischen 120 und 2200C in 10 K-Schritten variiert. Die Messergebnisse zu Selektivität, Umsatz und CO-Endkonzentration sind in der folgenden Tabelle widergegeben.
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 gκ 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.
In diesem Beispiel wird das sehr breite Temperaturfenster, in dem der Katalysator betrieben werden kann, deutlich.In this example, the very wide temperature window in which the catalyst can be operated becomes clear.
Beispiele 4Examples 4
Der erfindungsgemäße Katalysator nach Beispiel 1 wurde bei der Belastung von 2,5 l gKat "1 h"1 und der folgenden Gaszusammensetzung (33 Vol.-% H2; 25 Vol.-% H2O; 28,25 Vol.% N2; 13 Vol.-% CO2; 0,25 Vol.-% CO; 0,5 Vol.-% CH4) über eine Laufzeit von 1.000 h bei einer Temperatur von konstant 175°C betrieben. Es wurde über die Laufzeit eine CO-Ko nzentration von <50 ppm realisiert. Über die Laufzeit blieb CO2 jeweils von der Reaktion unberührt. Die Konzentration von 50 ppm CO gilt als Grenzwert für den Betrieb von Brennstoffzellen auf Basis Polymerelektrolytmembranen.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.
Die Entwicklung der CO-Komzentration in Abhängigkeit von der Zeit ist aus Diagramm 3 ersichtlich.The evolution of the CO concentration as a function of time is shown in Diagram 3.
Im Anschluss an den Versuch wurde die Temperatur der Reaktion variiert. Die Ergebnisse sind aus nachstehender Tabelle ersichtlich:Following the experiment, the temperature of the reaction was varied. The results are shown in the following table:
Das Beispiel unterstreicht die Langzeitstabilität des Katalysators.
Beispiel 5The example emphasizes the long-term stability of the catalyst. Example 5
Der erfindungsgemäße Katalysator nach Beispiel 1 wurde in Serie zu einem kommer- ziell einsetzbaren Katalysator für die Tieftemperaturkonvertierung betrieben. Dabei erfuhr der Katalysator für die selektive Methanisierung eine Belastung von 2,5 l gκat "1 h"1.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 gκ at "1 h " 1 .
Die Ein- und Ausgangswerte für beide Reaktionsstufen sind aus nachstehender Tabelle ersichtlich. Beispiel 5 a) zeigt die Werte bei dem Betrieb eines TTK-Katalysators bei 2100C, 5 b) die beim Betrieb eines TTK-Katalysators bei 2200C.The input and output values for both reaction stages are shown in the table below. 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.
CO CO2 H2 N2 H2O CH4 CO 2 CO 2 H 2 N 2 H 2 O CH 4
Ausgangoutput
Methani-Methani-
20 ppm 15,9 VoI. % 43,7 VoI % 40,3 VoI. % trocken 0, 14 VoI .% sierung20 ppm 15.9 VoI. % 43.7 VoI% 40.3 VoI. % dry 0, 14% vol
175°C175 ° C
Ausgangoutput
Methani-Methani-
44 ppm 15,8 VoI. % 43,7 VoI % 40,3 VoI. % trocken 0 ,2 Vol. % sierung44 ppm 15.8 VoI. % 43.7 VoI% 40.3 VoI. % dry 0, 2 vol.% sation
1900C190 0 C
Ausgangoutput
Methani-Methani-
46 ppm 15,8 VoI. % 43,4 VoI % 40,6 VoI. % trocken 0 ,3 Vol. % sierung46 ppm 15.8 VoI. % 43.4% VoI% 40.6 VoI. % dry 0, 3 vol.% sation
2000C200 0 C
Ausgangoutput
Methani-Methani-
16C ppm 15,4 VoI. % 42,4 VoI % 41 ,6 VoI. % trocken 0 ,6 Vol. % sierung16C ppm 15.4 VoI. % 42.4 VoI% 41, 6 VoI. % dry 0, 6 vol.% sation
210°C210 ° C
Beispiel 6Example 6
Der erfindungsgemäße Katalysator nach Beispiel 1 wurde einer Reihe von Atmosphärenwechseln unter Betriebsbedingungen unterzogen. Dabei wurde bei konstanter Reaktortemperatur von 175°C von einer Gaszusammensetzung 1 (2,5 l gκat "1 h"1, 33 Vol.-% H2; 25 Vol.-% H2O; 28,25 Vol.% N2; 13 Vol.-% CO2; 0,25 Vol.-% CO; 0,5 Vol.-% CH4) nach kurzer Spülung mit Stickstoff auf Luft umgestellt. Nach erneuter Stickstoffspülung wurde wieder auf die ursprüngliche Gaszusammensetzung 1 umgestellt.The inventive catalyst according to Example 1 was subjected to a series of atmospheric changes under operating conditions. In this case, at a constant reactor temperature of 175 ° C., a gas composition 1 (2.5 l gκ 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.
Dieses Verfahren testet die Belastbarkeit des Katalysators bei typischen Anfahr- und Abschaltprozessen in einer PEM-Brennstoffzelle. In der nachstehenden Tabelle sind die Umsatz- und Selektivitätswerte sowie die resultierende CO-Konzentration nach den einzelnen Atmosphärenwechseln aufgetragen:This procedure tests the load capacity of the catalytic converter during typical startup and shutdown processes in a PEM fuel cell. In the table below, the conversion and selectivity values and the resulting CO concentration are plotted according to the individual atmospheric changes:
Aus dem Beispiel geht klar hervor, dass der Katalysator stabil trotz Atmosphärenwechsel die Grenzkonzentration an CO von unter 50 ppm deutlich unterbietet.
From the example, it is clear that the catalyst is stable despite the change in atmosphere significantly undercuts the limit concentration of CO of less than 50 ppm.
Claims
1. Katalytisch aktive Zusammensetzung für die selektive Methanisierung von Kohlen- monoxid, dadurch gekennzeichnet, dass sie als Aktivkomponente wenigstens ein Element, ausgewählt aus der Gruppe bestehend aus Ruthenium, Rhodium, Nickel und Cobalt, und ein Trägermaterial auf Kohlebasis enthält.1. Catalytically active composition for the selective methanation of carbon monoxide, 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.
2. Katalytisch aktive Zusammensetzung gemäß Anspruch 1 , dadurch gekennzeichnet, dass die Aktivkomponente und/oder das Trägermaterial mit wenigstens einem EIe- ment, ausgewählt aus der Gruppe bestehend aus Eisen, Niob, Mangan, Molybdän und Zirkonium, dotiert sind.2. Catalytically active composition according to claim 1, characterized in that the active component and / or the carrier material with at least one EIe- ment, selected from the group consisting of iron, niobium, manganese, molybdenum and zirconium doped.
3. Katalytisch aktive Zusammensetzung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Aktivkomponente Ruthenium ist.3. Catalytically active composition according to claim 1 or 2, characterized in that the active component is ruthenium.
4. Katalytisch aktive Zusammensetzung gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass mit Eisen dotiert ist.4. Catalytically active composition according to one of claims 1 to 3, characterized in that it is doped with iron.
5. Katalytisch aktive Zusammensetzung gemäß einem der Ansprüche 1 bis 4, da- durch gekennzeichnet, dass die Gesamtbeladung des Trägermaterials mit der5. Catalytically active composition according to one of claims 1 to 4, characterized in that the total loading of the carrier material with the
Aktivkomponente 0,1 bis 20 Gew.-% beträgt.Active component 0.1 to 20 wt .-% is.
6. Verwendung einer katalytisch aktiven Zusammensetzung gemäß einem der Ansprüche 1 bis 5 für die selektive Methanisierung von Kohlenmonoxid.6. Use of a catalytically active composition according to any one of claims 1 to 5 for the selective methanation of carbon monoxide.
7. Verfahren zur selektiven Methanisierung von Kohlenmonoxid, dadurch gekennzeichnet, dass eine katalytisch aktive Zusammensetzung eingesetzt wird, die als Aktivkomponente wenigstens ein Element, ausgewählt aus der Gruppe bestehend aus Ruthenium, Rhodium, Nickel und Cobalt, und ein Trägermaterial auf Kohleba- sis enthält.7. A process for the selective methanation of carbon monoxide, characterized in that a catalytically active composition is used, which contains as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt, and a support material on Kohleba- sis.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Methanisierung in einem Temperaturbereich von 100 bis 300 °C erfolgt.8. The method according to claim 7, characterized in that the methanation takes place in a temperature range of 100 to 300 ° C.
9. Verwendung einer katalytisch aktiven Zusammensetzung gemäß einem der Ansprüche 1 bis 5 bei der Wasserstofferzeugung für Brennstoffzellenanwendungen.9. Use of a catalytically active composition according to any one of claims 1 to 5 in hydrogen production for fuel cell applications.
3 Fig. 3 Fig.
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DE102005003311A DE102005003311A1 (en) | 2005-01-24 | 2005-01-24 | Catalytically active composition for the selective methanation of carbon monoxide and process for its preparation |
PCT/EP2006/050312 WO2006077236A1 (en) | 2005-01-24 | 2006-01-19 | Catalytically active composition for the selective methanation of carbon monoxide and method for producing said composition |
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US (1) | US7560496B2 (en) |
EP (1) | EP1843844A1 (en) |
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EP2125204A1 (en) * | 2007-03-13 | 2009-12-02 | Umicore AG & Co. KG | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
EP2336083A1 (en) * | 2009-12-17 | 2011-06-22 | Topsøe Fuel Cell A/S | Gas generator and processes for the conversion of a fuel into an oxygen-depleted gas and/or hydrogen-enriched gas |
JP5662044B2 (en) * | 2010-03-31 | 2015-01-28 | 大阪瓦斯株式会社 | Method for determining the degree of activation of a catalyst |
DE102011085165A1 (en) | 2011-10-25 | 2013-04-25 | Wacker Chemie Ag | Process for the preparation of vinyl acetate |
JP5889613B2 (en) * | 2011-11-25 | 2016-03-22 | 国立大学法人群馬大学 | Metal-supported carrier, metal-supported catalyst, methanation reaction apparatus, and method related thereto |
DE102011121930A1 (en) * | 2011-12-22 | 2013-06-27 | Solarfuel Gmbh | methanation |
EP3072589A1 (en) | 2015-03-26 | 2016-09-28 | Basf Se | Catalyst and method for the selective methanation of carbon monoxide |
JP6800965B2 (en) * | 2015-10-05 | 2020-12-16 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | Methods for Producing Ruthenium / Iron / Carbon Carrier Catalysts |
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US3424808A (en) | 1967-10-03 | 1969-01-28 | Foster Grant Co Inc | Dehydrogenation and methanation catalyst and process |
US3615164A (en) | 1968-01-10 | 1971-10-26 | Bernard S Baker | Process for selective removal by methanation of carbon monoxide from a mixture of gases containing carbon dioxide |
US3847963A (en) * | 1973-02-01 | 1974-11-12 | Ventron Corp | Methanation processes |
JPS5216501A (en) * | 1975-07-30 | 1977-02-07 | Tokyo Gas Co Ltd | Process for manufacturing fuel gas of high calorific value |
DE3130805A1 (en) | 1981-08-04 | 1983-02-24 | Basf Ag, 6700 Ludwigshafen | NEW RUTHENIUM / COAL HYDRATING CATALYSTS, THEIR PRODUCTION AND USE FOR THE SELECTIVE HYDROGENATION OF UNSATURATED CARBONYL COMPOUNDS |
JPH0393602A (en) * | 1989-09-07 | 1991-04-18 | Asahi Chem Ind Co Ltd | Selective removing of carbon monoxide |
GB9609918D0 (en) | 1996-05-11 | 1996-07-17 | Johnson Matthey Plc | Hydrogen purification |
GB9620287D0 (en) | 1996-09-28 | 1996-11-13 | Johnson Matthey Plc | Carbon monoxide removal |
US6913738B1 (en) | 1999-03-05 | 2005-07-05 | Osaka Gas Co., Ltd. | System for removing carbon monoxide and method for removing carbon monoxide |
JP4460126B2 (en) | 2000-08-31 | 2010-05-12 | 出光興産株式会社 | Method for removing carbon monoxide from hydrogen-containing gas |
EP1246286A1 (en) | 2001-03-31 | 2002-10-02 | OMG AG & Co. KG | Combined heat and power apparatus with gas producing system and fuel cells and method of operation |
ATE378107T1 (en) * | 2001-12-07 | 2007-11-15 | Basf Ag | METHOD FOR PRODUCING RUTHENIUM/IRON/CARBON SUPPORTED CATALYSTS |
JP2004097859A (en) | 2002-09-04 | 2004-04-02 | Tokyo Inst Of Technol | Catalyst and method for eliminating carbon monoxide |
US7118717B2 (en) | 2002-09-06 | 2006-10-10 | Engelhard Corporation | Simplified article for carbon monoxide removal |
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