DE102015222972A1 - Catalyst and process for the preparation - Google Patents
Catalyst and process for the preparation Download PDFInfo
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- DE102015222972A1 DE102015222972A1 DE102015222972.6A DE102015222972A DE102015222972A1 DE 102015222972 A1 DE102015222972 A1 DE 102015222972A1 DE 102015222972 A DE102015222972 A DE 102015222972A DE 102015222972 A1 DE102015222972 A1 DE 102015222972A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 claims abstract description 68
- 239000000446 fuel Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 239000002737 fuel gas Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 238000010146 3D printing Methods 0.000 claims abstract description 5
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000002407 reforming Methods 0.000 claims description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000003466 welding Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000005755 formation reaction Methods 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J35/56—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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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
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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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
- B01J23/38—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
- B01J23/42—Platinum
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Katalysator (1), umfassend eine metallische Trägerstruktur (2, 2a–2z) sowie ein metallisches Katalysatormaterial (3, 3a, 3b), wobei das Katalysatormaterial (3, 3a, 3b) mit der Trägerstruktur (2, 2a–2z) verschweißt ist. Verfahren zur Herstellung eines Katalysators (1), wobei die Trägerstruktur (2, 2a–2z) schichtweise durch 3D-Druck aufgebaut wird, und/oder das Katalysatormaterial (3, 3a, 3b) in Form von Partikeln (3c–3f) an der Trägerstruktur (2, 2a–2z) angelagert und anschließend mit der Trägerstruktur (2, 2a–2z) verschweißt wird, und/oder das Katalysatormaterial (3, 3a, 3b) der Trägerstruktur (2, 2a–2z) in Form aufgeschmolzener Tropfen (3g) zugeführt wird. Reformer (10) zur Herstellung eines Wasserstoff (12a) enthaltenden Brenngases (12) für eine Brennstoffzelle (13, 13a–13c) aus einem Kohlenwasserstoff (11a) enthaltenden Brenngas (11) mit einem Katalysator (1) gemäß der Erfindung.Catalyst (1) comprising a metallic support structure (2, 2a-2z) and a metallic catalyst material (3, 3a, 3b), wherein the catalyst material (3, 3a, 3b) with the support structure (2, 2a-2z) is welded , A process for producing a catalyst (1), wherein the support structure (2, 2a-2z) is built up in layers by 3D printing, and / or the catalyst material (3, 3a, 3b) in the form of particles (3c-3f) on the Supported structure (2, 2a-2z) and then welded to the support structure (2, 2a-2z), and / or the catalyst material (3, 3a, 3b) of the support structure (2, 2a-2z) in the form of molten drops ( 3g) is supplied. Reformer (10) for producing a fuel gas (12) containing hydrogen (12a) for a fuel cell (13, 13a-13c) from a fuel gas (11) containing a hydrocarbon (11a) with a catalyst (1) according to the invention.
Description
Die vorliegende Erfindung betrifft Katalysatoren, die insbesondere in Reformern für Hochtemperaturbrennstoffzellen einsetzbar sind.The present invention relates to catalysts which can be used in particular in reformers for high-temperature fuel cells.
Stand der Technik State of the art
Katalysatoren bestehen häufig aus einer Trägerstruktur aus einem preiswerten Grundwerkstoff, auf der ein edles Katalysatormaterial aufgebracht ist. Eine solche Trägerstruktur kann beispielsweise ein dreidimensionales Gitter sein. Derartige Katalysatoren sind beispielsweise aus der
Eine feste Verbindung zwischen dem Katalysatormaterial und dem Grundwerkstoff lässt sich gemäß der
Soll der Katalysator beispielsweise in einem Reformer eingesetzt werden, der ein Brenngas für eine Hochtemperatur-Brennstoffzelle aufbereitet, so muss er mindestens Temperaturen von 500–600 °C standhalten. Durch diese Temperaturen sowie durch die häufigen Temperaturwechsel beim An- und Abfahren der Brennstoffzelle wird die Verbindung zwischen dem Grundwerkstoff und dem Katalysatormaterial stark belastet. Ist diese Verbindung nicht fest genug, kann das Katalysatormaterial abplatzen und in den Gaskreislauf der Brennstoffzelle gelangen.If the catalyst is to be used, for example, in a reformer, which processes a fuel gas for a high-temperature fuel cell, it must withstand at least temperatures of 500-600 ° C. These temperatures as well as the frequent temperature changes when starting and stopping the fuel cell, the connection between the base material and the catalyst material is heavily loaded. If this compound is not strong enough, the catalyst material can flake off and get into the gas cycle of the fuel cell.
Offenbarung der Erfindung Disclosure of the invention
Im Rahmen der Erfindung wurde ein Katalysator entwickelt. Dieser Katalysator umfasst eine metallische Trägerstruktur sowie ein metallisches Katalysatormaterial.In the context of the invention, a catalyst was developed. This catalyst comprises a metallic carrier structure as well as a metallic catalyst material.
Erfindungsgemäß ist das Katalysatormaterial mit der Trägerstruktur verschweißt. Das Katalysatormaterial kann insbesondere durch Auftragschweißen auf die Trägerstruktur aufgebracht sein.According to the invention, the catalyst material is welded to the carrier structure. The catalyst material may in particular be applied to the carrier structure by build-up welding.
Schweißen ist eine unlösbare metallische Verbindung unter Anwendung von Wärme. Die Erfinder haben erkannt, dass die zum Verschweißen nötige große Hitze eine besonders hohe Potentialbarriere darstellt, die zum Trennen des Katalysatormaterials von der Trägerstruktur zu überwinden ist. Die zum Verschweißen nötigen Temperaturen liegen höher als der Schmelzpunkt des metallischen Katalysatormaterials und/oder der metallischen Trägerstruktur, und somit deutlich höher als die Betriebstemperatur eines Reformers für eine Hochtemperaturbrennstoffzelle. In diesem Temperaturbereich ist somit nicht zu befürchten, dass das Katalysatormaterial von der metallischen Trägerstruktur abplatzt.Welding is a permanent metallic bond using heat. The inventors have recognized that the high heat required for welding constitutes a particularly high potential barrier which has to be overcome for separating the catalyst material from the carrier structure. The temperatures required for welding are higher than the melting point of the metallic catalyst material and / or the metallic support structure, and thus significantly higher than the operating temperature of a reformer for a high-temperature fuel cell. In this temperature range is therefore not to be feared that the catalyst material flakes off the metallic support structure.
Hingegen wird bei der chemischen Gasphasenabscheidung (CVD) nach dem bisherigen Stand der Technik lediglich ein durch eine chemische Reaktion aus einem Vorläufermaterial (Precursor) gebildetes Beschichtungsmaterial auf der Trägerstruktur adsorbiert. Bei der physikalischen Gasphasenabscheidung (PVD) wird ein verdampftes Beschichtungsmaterial auf der Trägerstruktur adsorbiert. Beiden Verfahren ist gemein, dass das Beschichtungsmaterial im Vergleich zum Schweißen unter Anwendung einer wesentlich geringeren Wärmemenge aufgebracht wird. Dementsprechend geringer ist die Potentialbarriere, die einer Desorption, bzw. einem Abplatzen, des Beschichtungsmaterials entgegensteht.On the other hand, in chemical vapor deposition (CVD) of the prior art, only a coating material formed by a chemical reaction from a precursor material is adsorbed on the support structure. In physical vapor deposition (PVD), a vaporized coating material is adsorbed on the support structure. Both methods have in common that the coating material is applied compared to welding using a much smaller amount of heat. Accordingly, the potential barrier is lower, which precludes desorption or spalling of the coating material.
Gleiches gilt für das Einbrennen, bei dem das Beschichtungsmaterial nach dem Aufbringen durch Wärmeanwendung entweder in sich oder mit der Trägerstruktur vernetzt und somit verfestigt wird.The same applies to the stoving, in which the coating material is crosslinked after application by application of heat either in itself or with the support structure and thus solidified.
Die Trägerstruktur kann beispielsweise als Gitter ausgebildet sein. Sie kann insbesondere aus Tantal, einer Chromoxid bildenden Eisenlegierung oder einer Aluminiumoxid bildenden Eisenlegierung bestehen. Diese Materialien sind hochwarmfest und somit für den Einsatz in Hochtemperaturbrennstoffzellen tauglich.The support structure may be formed, for example, as a grid. It may in particular consist of tantalum, a chromium oxide-forming iron alloy or an aluminum oxide-forming iron alloy. These materials are heat resistant and thus suitable for use in high temperature fuel cells.
Das Katalysatormaterial vermag vorteilhaft die Reformierung eines gasförmigen Kohlenwasserstoffs zu Wasserstoff und einem Kohlenoxid zu katalysieren. Das primär von einer Hochtemperaturbrennstoffzelle verwertbare Brennstoff ist Wasserstoff. Wasserstoff ist jedoch ein Sekundärenergieträger, der in der Natur nur in gebundener Form vorkommt, beispielsweise in langkettigen Kohlenwasserstoffmolekülen in Erdgas. Indem ein gasförmiger Kohlenwasserstoff in Erdgas oder einem anderen Brenngas zu Wasserstoff und mindestens einem Kohlenoxid reformiert wird, kann der Wasserstoff für den Betrieb der Brennstoffzelle nutzbar gemacht werden. Das Kohlenoxid kann beispielsweise Kohlenmonoxid oder Kohlendioxid sein. Das Katalysatormaterial kann insbesondere beispielsweise Gold oder Platin sein.The catalyst material may advantageously catalyze the reforming of a gaseous hydrocarbon to hydrogen and a carbon monoxide. The fuel that can primarily be used by a high-temperature fuel cell is hydrogen. However, hydrogen is a secondary energy carrier that occurs only in bound form in nature, for example in long-chain hydrocarbon molecules in natural gas. By reforming a gaseous hydrocarbon in natural gas or other fuel gas to hydrogen and at least one carbon monoxide, the hydrogen can be harnessed for operation of the fuel cell. The carbon monoxide may be, for example, carbon monoxide or carbon dioxide. The catalyst material may in particular be, for example, gold or platinum.
In einer besonders vorteilhaften Ausgestaltung der Erfindung besteht die Trägerstruktur aus dem Katalysatormaterial. Dann unterscheiden sich die thermischen Ausdehnungskoeffizienten von Trägerstruktur und Katalysatormaterial nicht, so dass bei Temperaturwechseln die Verbindung zwischen Trägerstruktur und Katalysatormaterial insoweit nicht belastet wird. Beispielsweise kann ein regelmäßiges Gitter aus dem Katalysatormaterial zusätzliche Anformungen aus dem Katalysatormaterial aufweisen, und/oder die aus dem Katalysatormaterial gebildeten Gitterstreben können Aussparungen aufweisen. Beide Maßnahmen vergrößern die spezifische Oberfläche des Katalysatormaterials pro Einheit Masse. Da insbesondere Edelmetalle sehr kostbar sind, wird hierdurch die Wirtschaftlichkeit des Katalysators verbessert.In a particularly advantageous embodiment of the invention, the support structure consists of the catalyst material. Then the coefficients of thermal expansion of the support structure and the catalyst material do not differ, so that in the case of temperature changes, the connection between the support structure and the catalyst material is not burdened in this respect. For example, a regular Grid from the catalyst material have additional projections of the catalyst material, and / or the lattice struts formed from the catalyst material may have recesses. Both measures increase the specific surface area of the catalyst material per unit mass. Since, in particular, precious metals are very precious, this improves the efficiency of the catalyst.
Die Erfindung bezieht sich auch auf Herstellungsverfahren für den Katalysator. Eine erste Ausgestaltung sieht vor, dass die Trägerstruktur schichtweise durch 3D-Druck aufgebaut wird. Dies ist insbesondere dann vorteilhaft, wenn die Trägerstruktur aus dem Katalysatormaterial besteht und dessen spezifische Oberfläche vergrößert werden soll. Alle Anformungen, Aussparungen und sonstigen filigranen Strukturen des Katalysatormaterials können dann von vornherein in das zu druckende 3D-Modell einbezogen werden. Der Katalysator lässt sich dann mit all diesen Strukturen einstückig fertigen.The invention also relates to production processes for the catalyst. A first embodiment provides that the carrier structure is built up in layers by 3D printing. This is particularly advantageous if the support structure consists of the catalyst material and its specific surface area is to be increased. All formations, recesses and other filigree structures of the catalyst material can then be included in the 3D model to be printed from the outset. The catalyst can then be manufactured in one piece with all these structures.
In einer weiteren besonders vorteilhaften Ausgestaltung des Verfahrens wird das Katalysatormaterial in Form von Partikeln an der Trägerstruktur angelagert und anschließend mit der Trägerstruktur verschweißt. Dies ist insbesondere vorteilhaft, um auch das Innere einer dreidimensionalen Trägerstruktur mit Katalysatormaterial zu belegen. Das Anlagern kann beispielsweise dadurch unterstützt werden, dass zwischen den Partikeln und der Trägerstruktur eine elektrostatische oder magnetische Kraft wirkt.In a further particularly advantageous embodiment of the method, the catalyst material is deposited in the form of particles on the support structure and then welded to the support structure. This is particularly advantageous in order to also cover the interior of a three-dimensional support structure with catalyst material. The attachment may be assisted, for example, by an electrostatic or magnetic force acting between the particles and the support structure.
Das Verschweißen kann mit einem seriell arbeitenden Verfahren erfolgen, beispielsweise indem die angelagerten Partikel durch einen Laserstrahl mit der Trägerstruktur verschweißt werden. Es kann jedoch beispielsweise auch die Trägerstruktur mitsamt den angelagerten Partikeln als Ganzes erwärmt werden, beispielsweise in einem Ofen oder durch einen Stromfluss, der durch die Trägerstruktur geleitet wird. Dies ist ein paralleles Verfahren, das deutlich schneller arbeitet.The welding can be carried out by a serial method, for example by the deposited particles are welded by a laser beam to the support structure. However, it is also possible, for example, to heat the support structure together with the deposited particles as a whole, for example in an oven or through a current flow which is conducted through the support structure. This is a parallel process that works much faster.
Die Partikel aus dem Katalysatormaterial können der Trägerstruktur in einer weiteren besonders vorteilhaften Ausgestaltung der Erfindung beispielsweise in einer Lösung und/oder in einer Suspension zugeführt werden. Dann kann die Trägerstruktur beispielsweise als Ganzes in die Lösung bzw. die Suspension eingetaucht werden, so dass sie überall gleichzeitig mit Partikeln aus dem Katalysatormaterial belegt wird. Die Lösung bzw. die Suspension erreicht vorteilhaft beispielsweise auch das Innere eines dreidimensionalen Gitters.The particles of the catalyst material can be supplied to the carrier structure in a further particularly advantageous embodiment of the invention, for example in a solution and / or in a suspension. Then, the carrier structure can be immersed, for example, as a whole in the solution or the suspension, so that it is everywhere occupied at the same time with particles of the catalyst material. The solution or suspension advantageously also reaches, for example, the interior of a three-dimensional grid.
Analoges gilt in einer weiteren besonders vorteilhaften Ausgestaltung der Erfindung, in der die Partikel aus dem Katalysatormaterial der Trägerstruktur in einem Gasstrom zugeführt werden.The same applies in a further particularly advantageous embodiment of the invention, in which the particles are fed from the catalyst material of the support structure in a gas stream.
In einer weiteren besonders vorteilhaften Ausgestaltung der Erfindung wird das Katalysatormaterial der Trägerstruktur in Form aufgeschmolzener Tropfen zugeführt. In diesen Tropfen ist dann bereits mindestens ein Großteil der Wärme enthalten, die für das Verschweißen mit der Trägerstruktur nötig ist. Weiterhin können die Tropfen sich unmittelbar an die Formgebung der Trägerstruktur anpassen.In a further particularly advantageous embodiment of the invention, the catalyst material is supplied to the carrier structure in the form of molten drops. At least a large part of the heat which is necessary for welding to the carrier structure is then already contained in these drops. Furthermore, the drops can be adapted directly to the shape of the support structure.
Vorteilhaft wird die Trägerstruktur bei der Herstellung des Katalysators beheizt. Dann wird auf diesem Wege ein Teil der Wärme zugeführt, die für das Verschweißen des Katalysatormaterials mit der Trägerstruktur notwendig ist. Wird das Katalysatormaterial beispielsweise in Form aufgeschmolzener Tropfen zugeführt, brauchen diese dann nur noch eine geringere Temperatur zu haben.Advantageously, the support structure is heated in the preparation of the catalyst. Then, in this way, a part of the heat is supplied, which is necessary for the welding of the catalyst material with the support structure. If the catalyst material is supplied, for example, in the form of molten drops, then these need only have a lower temperature.
Nach dem zuvor Gesagten bezieht sich die Erfindung auch auf einen Reformer zur Herstellung eines Wasserstoff enthaltenden Brenngases für eine Brennstoffzelle aus einem Kohlenwasserstoff enthaltenden Brenngas. Dieser Reformer zeichnet sich dadurch aus, dass zur Katalyse des Kohlenwasserstoffs zu Wasserstoff und mindestens einem Kohlenoxid ein Katalysator gemäß der Erfindung vorgesehen ist. Dadurch ist der Reformer zum Einen einfacher und preiswerter herstellbar und zum Anderen dauerhaltbarer, insbesondere wenn er häufig an- und abgefahren wird, was mit einer Aufheizung auf typischerweise 500–600 °C bzw. einer Abkühlung auf Umgebungstemperatur verbunden ist.From the above, the invention also relates to a reformer for producing a hydrogen-containing fuel gas for a fuel cell from a hydrocarbon-containing fuel gas. This reformer is characterized in that a catalyst according to the invention is provided for catalyzing the hydrocarbon to hydrogen and at least one carbon monoxide. As a result, the reformer on the one hand easier and cheaper to produce and on the other durable, especially if he is frequently on and off, which is associated with a heating to typically 500-600 ° C or a cooling to ambient temperature.
Die Trägerstruktur kann beispielsweise ein regelmäßiges dreidimensionales Gitter mit einer Periode von 0,1 mm sein, wobei die Dicke der Gitterstege geringer ist als diese Periode, um das Gitter für ein gasförmiges Medium durchgängig zu halten. Das Gitter kann beispielsweise die Form eines Kreiszylinders mit einem Durchmesser von 40 cm und einer Höhe von 5 cm ausfüllen.The support structure may be, for example, a regular three-dimensional grid with a period of 0.1 mm, the thickness of the grid bars being less than this period in order to keep the grid continuous for a gaseous medium. For example, the grid may be in the shape of a circular cylinder having a diameter of 40 cm and a height of 5 cm.
Weitere, die Erfindung verbessernde Maßnahmen werden nachstehend gemeinsam mit der Beschreibung der bevorzugten Ausführungsbeispiele der Erfindung anhand von Figuren näher dargestellt. Further measures improving the invention will be described in more detail below together with the description of the preferred embodiments of the invention with reference to figures.
Ausführungsbeispieleembodiments
Es zeigt: It shows:
Nach
An einer Vielzahl von Orten ist Katalysatormaterial
Die Brennstoffzelle
ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
Zitierte PatentliteraturCited patent literature
- US 6878351 B1 [0002] US 6878351 B1 [0002]
- US 8226817 B1 [0002] US 8226817 B1 [0002]
- EP 2875859 A1 [0002] EP 2875859 A1 [0002]
- EP 0699474 A2 [0002] EP 0699474 A2 [0002]
- EP 1663481 B1 [0003] EP 1663481 B1 [0003]
- DE 19950521 A1 [0003] DE 19950521 A1 [0003]
Claims (12)
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