CA2384606A1 - A noble metal-containing supported catalyst and a process for its preparation - Google Patents
A noble metal-containing supported catalyst and a process for its preparation Download PDFInfo
- Publication number
- CA2384606A1 CA2384606A1 CA002384606A CA2384606A CA2384606A1 CA 2384606 A1 CA2384606 A1 CA 2384606A1 CA 002384606 A CA002384606 A CA 002384606A CA 2384606 A CA2384606 A CA 2384606A CA 2384606 A1 CA2384606 A1 CA 2384606A1
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- Canada
- Prior art keywords
- support material
- supported catalyst
- catalyst according
- catalyst
- noble metal
- Prior art date
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- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 33
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 16
- 239000002923 metal particle Substances 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 241000872198 Serjania polyphylla Species 0.000 claims 2
- 229910001260 Pt alloy Inorganic materials 0.000 claims 1
- 229910000929 Ru alloy Inorganic materials 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 101150087654 chrnd gene Proteins 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010923 batch production Methods 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004886 process control Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910002849 PtRu Inorganic materials 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- -1 zoolit~ Chemical compound 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000011514 reflex Effects 0.000 description 2
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 101100537937 Caenorhabditis elegans arc-1 gene Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001550206 Colla Species 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- 235000017274 Diospyros sandwicensis Nutrition 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 241000282838 Lama Species 0.000 description 1
- 241000492493 Oxymeris Species 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- XDXHAEQXIBQUEZ-UHFFFAOYSA-N Ropinirole hydrochloride Chemical compound Cl.CCCN(CCC)CCC1=CC=CC2=C1CC(=O)N2 XDXHAEQXIBQUEZ-UHFFFAOYSA-N 0.000 description 1
- 240000002871 Tectona grandis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
Classifications
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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
- 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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- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J35/23—
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- B01J35/30—
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- B01J35/33—
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- B01J35/392—
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- B01J35/393—
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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
- B01J37/02—Impregnation, coating or precipitation
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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
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
Abstract
The invention provides a noble metal-containing supported catalyst which contains one of the noble metals from the group Au, Ag, Pt, Pd, Rh, Ru, Ir, Os or alloys of one or more of these noble metals in the form of noble metal particles on a powdered support material. The particles deposited on the support material have a degree of crystallinity, determined by X-ray diffraction, of more than 2 and an average particle size between 2 and 10 mm. The high crystallinity and the small particle size of the noble metal particles lead to high catalytic activity for the catalyst. It is particularly suitable for use in fuel cells and for the treatment of exhaust gases from internal combustion engines.
Description
A NOBLE METAL-CONTAINING SUPPORTED CATAL'~IST
AND A PROCESS FOR fTS PREPARATION
~'L>Q OF~,~E jNV~TION
The presaait invcation provides a noble metal-cordaiaiug supported catalyst which contains a noble metal selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os and nuxturea thettof and a process for the preparation thereof.
~~C,1~GRQrTN,~ O~ Tl'~E rIVVEN1'ION
Noble metal-containing supported catalysts are used in many industrial fields such as, for example, the synti~esis of chemical eompaunds, the ecmversiont of harmful substances in the exhaust gases from internal combustion engines and as electrocatalysts for fuel cells, to mention only a few fields of application.
?o produce the highest possible catalytic activity for the noble aaetal, they have an be applied to the surface of the parricular support material in the highest poss~'ble dispersion with particle sizes in the range betwe~ 1 and 15 rm. A small particle size in itself, however, is not a guarantee of high activity. A poorly developed crystal structure in the platinum particles thus also leads to diminished catalytic activity.
Similar considerations also apply to the quality of alloy formation of aDoy catalysts. It is known in the art that ternary alloy cafial~rsts for fuel cells with an ordered crystal structure have a catalytio activity for the electrocherrtical reduction of oxygen which is at least twice as great as that of a non~alloyed platinum catalyst.
The catalyst is prepared by depositing the alloy components on the support tnatarial by impregnation.
Tlre ahoy is formed by thermal treatment at 900°C for a period of one hour under err atmosphere of nitrogen.
Support nlate~rials which are used for supported catalysts include a variety of materials. 1n gerr~al, the support materials, depending on the ;Seld of application, all have a high specific surface area, the so-called BET surface area (measured by rtitrogcxr adsorption, is accordance with DTN b6132), of more than 14 mz/g. For furl cells, electrically conductive carbon materials are used as supgortg for the catalytically active components. In the case of car e7ch~aust catalysis, however, oxidie support materials such as, for example, active aluminium oxides (for example y-aluminium oxide), aluminium silicate, zoolit~, titanium oxide, zireoaiu>n oxide, rare earth oxides or mixtures or mixed oxidca thereof are used.
Precursor compounds of the c~talytically active eomponants afro deposited on the sarface of these materials and are converted into the final catalykically active form by subs~ucnt thermal treatment. The oneness of distribution (dis~ioa) of the catalytieally active particles in the final catalyst, aid thus the catalytic metal surface area available for the catalytic process, depends critically on rlte type of process and method used for these two processes (deposition and thernnal treatment).
A variety of processes has been disclosed for deposition of the catalytically active compon~cats on the powdm~ad support material. These include, for example, impregnation with an excess of impregnation solution. hu this case an aqueous solution of the eatalytically active components is added to the powdorcd support material, when the volume of the solution may he substau'ally greater than the water absorption capacity of the support material. Thus a material is pmdu~cod which has a thick pasty 1 S consistency and which is dewatered, for example, in as oven at elevated tezaperatures of 80 to 150°C. Chromatographic effects may take place durhrg the dewatering of this material which can load to non-uniform distribution of the catalyticahy active components on the support matacial.
For pore volume impregnation, an amount of solvent is used to dissolve the catalytically active components which cozr~ponds to abort ?0 to 110 % of the absorption capacity of the support material for this solvent. The solvent is generally vuater. This solution is distributed as uniformly as possible, for example by spraying over the support material which is being rolled about in a teak. Altar distribution of the entire solution oven tbve support materiel the latter is still frce~-flowing, ddapite the water content. Chromatographic efforts can be largely avoided using pore volume impregnation. This mt~od usually provides better results titan the impregnation process using as excess of solvent described above.
For a proacas for so-called hpmogea~eous deposition from sohttion, the support material is first suspended inn, for example, water. Then an aqueous solution of precursor compounds of the catalyticahy active cod is added using capillary injection with constant stirring. Capillary infection is understood tv be the slow addition of the solution uncle; the surface of the suspension of support material, using a capillary. As fast and as homogeneous a distribution as possible of the prxursor compounds over the entire volume of the suspension is intended to be crnsurad by intensive stinting and slow addition. Here, some adearption of the poor compounds, and thus the fornaationt of crystallisation seeds, takes place at the surface of the support material. The extent of this adsorption depends on the combination of support material acrd precursor compound. With material combinations which do not ensure adequate adsorption of the precursor compounds on the support material, or when chemical fixing of the catalytacally active cxymponents to the support material as desired, the precursor compounds can be precipitated on the support material by capillary injection of a base into the suspension of the support material.
To complete preparation of the catalyst material, the support material coated with the catalytically active components is subjected to a subsequent thermal tnarmant which converts the precursors of the catalytieally active components into the catalytically active form and optionally leads to the foraratian of an alloy Temperatures of more than 300°C up to 1000°C and trcatament times of 0.5 to 3 hours are required for this. Typically, batch processes are used for this in which the catalyst material is agglonnerated and the noble metal particles become coarser due to the long treatme»t times and the siat~ effects which take place. Noble metal particles up to 50 nm or larger eau develop in this way. To form an alloy, temp~auur~ above 900°C and treatrncnt times of at least 0.5 hours are usually required, whcrain there is a risk of excessive particle growth due to sintering.
However, it is iaipo=tant that the catalysts have as higb a surface arcs as possible (i.e. high dispersion) on the support in order to ensure high catalytic activity. Catalysts with average particle sizes for the nobly metals of more them 20 nm are usually not vary active.
Support materials coeted wills catalysts using known ~c~scsj for tneahnent 2S cannot simultaneously comply wills the conflicting requirements for well deveiop~!
crystallinity or alloy structure sad small average particle diameters far the noble metal particles.
In an alternative pmceas for the thermal troatme~nt of powde~rod eubsiances the powdered substances arc traet~ in a high temperahue flow rtactos. The treatmanc temp~atwre is the flow reactor may be higher than 1000°C. Tha time of tre~atma~nt may 6e varied between 0.01 seconds and a few minutes. Finely dispersed noble motels can then be deposited on, for example, aluminium oxide.
rt has also been suggested that a turbulent or laminar burner be used as an eaaandal source of heat. The process is thus performed is an oxidizing aanosphere and is not suitable for preparing catalysts on sttpporc materials made of carbon (graphite, carbon black), such as those used for fuel calls. The carbon black support would be oxidized and some would be burnt away.
Based on the forgoing, there is a need in the art for methods of preparing a noble mewl-containing supported catalysts which have a high txystalliaity ox a well-developed alloy saucture. 'There is also a need for noble metal-containing supported catalysts that have a small particle size and high dispersion.
SUMMARY OF ~~',,J~IY~'I~?N
The present invention provides a noble ~xrrtal-containing supported catalyst which eoataxna ane of the noble mceals from the group Au, Ag, Pt, Pd, Rh, Ru,1r, Os or alloys of one or more of these metals on a powdered support material. The supported catalyst contains particles of noble metal deposited on the support material having a relative degree of crystallinity Cue, determined by ~C-ray diffiaetion, of more than 2, preferably morn than 5, and an average particle size between 2 and 10 nm.
For a bettor understanding of the presort invatdioa together with other and further advantages and enabOdimenta, rats is made to tine Following description taken in eonjut~tion with the examples, the accopc of the which is set forth in the appended claims.
F
The prefaced embodiments of the iaves~tion have been ebosnnt for purposes of illustration and description but are not intended to restrict the scope of the invention in any way, The prefemad embodiments of ceatain affects of the invention era shown in the accompanying figure, wherein:
Figure 1 illustrates an apparatus for thermal tt~ratmesrt of the catalyst precursor to prepare the catalyst of the euxrent invention.
D
The present inveuntion will now be des'Cribed in coninection with pre~d embodiriaents. These embodiments are presented to aid in au understanding of the present invention and are not intended to, and should not be construed, to limit the invention in any way. All alternatives, modifications and equivalents that may become obvious to those of ordinary skill upon reading the disclosure are included within the sprit and ~;ope of the present invtntian, This disclosure is not a primer on pring noble matal-containing supportcd catalysts, basic concepts known to those skilled in the art hava not been set forth in detail.
'1"he catalyst according to the invcntion, due to the thermal treatment which is described below, has a very high crystallinity, filae relative degrec of cxystallinity Cx, which cats be determined by radiographic measurements, was introduced by the inventors for the Quantitative determination of crystallinity: It is de8»ed by equation (1):
~x ~~ (1) I, The rclative degree of cryatalliaity is dete3mined by radiagsnphic measurements on powdered sanaplea (powder diffractomcter from the Stoe Co., copper Kcc radiation). rn equation ( 1 ) Ix rcprescnts the intensity of a specific diffraction reflex (measured in counts) from the catalyst sample. rn the case of platinum, for example, the (hkl 111 reflcx is ~, which can be regarded as a measure of high electrochemical activity for the reduction of oxygen. l, is the intetwity of x-ray diffraction from an K'ra~
amorphous standard with the sauna composition as the catalyst sample, wherein the inta~sity of the X-ray diffraction reflex from the sample is determined at the same angle as for the sample. Itt the case of a carbon supported platinum sample, the amorphous standard is a material with a particle size for the platinum of less than 2 um which no longer exht'bits any X-ray diffraction retlaxcs.
Dc~nding on the intended application of the catalyst, different support matcrials can be used. For use as anode or cathode catalysts in fuel cells, electrically cosxductive support materials basal on carbon from the group carbon black, graphite, active carbon and fibrous, graphitic nertotubes arc normally used. For car cxhaust gas catalysts, on the other hand, oxidic materials from the group of active aluminium oxide, aluminium silicate, zoolitc, titanium oxide, zirconium oxide, rare earth oxides or mixtures or mixed oxides thexeaf are used. Furthermorc, the noblc metals in the catalyst may also be alloyed with at least one bast metal fraxu the group Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu and Zen. These base metals act as promoters, that is they nnodif~
the catalytic effect of the noble metal.
AND A PROCESS FOR fTS PREPARATION
~'L>Q OF~,~E jNV~TION
The presaait invcation provides a noble metal-cordaiaiug supported catalyst which contains a noble metal selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os and nuxturea thettof and a process for the preparation thereof.
~~C,1~GRQrTN,~ O~ Tl'~E rIVVEN1'ION
Noble metal-containing supported catalysts are used in many industrial fields such as, for example, the synti~esis of chemical eompaunds, the ecmversiont of harmful substances in the exhaust gases from internal combustion engines and as electrocatalysts for fuel cells, to mention only a few fields of application.
?o produce the highest possible catalytic activity for the noble aaetal, they have an be applied to the surface of the parricular support material in the highest poss~'ble dispersion with particle sizes in the range betwe~ 1 and 15 rm. A small particle size in itself, however, is not a guarantee of high activity. A poorly developed crystal structure in the platinum particles thus also leads to diminished catalytic activity.
Similar considerations also apply to the quality of alloy formation of aDoy catalysts. It is known in the art that ternary alloy cafial~rsts for fuel cells with an ordered crystal structure have a catalytio activity for the electrocherrtical reduction of oxygen which is at least twice as great as that of a non~alloyed platinum catalyst.
The catalyst is prepared by depositing the alloy components on the support tnatarial by impregnation.
Tlre ahoy is formed by thermal treatment at 900°C for a period of one hour under err atmosphere of nitrogen.
Support nlate~rials which are used for supported catalysts include a variety of materials. 1n gerr~al, the support materials, depending on the ;Seld of application, all have a high specific surface area, the so-called BET surface area (measured by rtitrogcxr adsorption, is accordance with DTN b6132), of more than 14 mz/g. For furl cells, electrically conductive carbon materials are used as supgortg for the catalytically active components. In the case of car e7ch~aust catalysis, however, oxidie support materials such as, for example, active aluminium oxides (for example y-aluminium oxide), aluminium silicate, zoolit~, titanium oxide, zireoaiu>n oxide, rare earth oxides or mixtures or mixed oxidca thereof are used.
Precursor compounds of the c~talytically active eomponants afro deposited on the sarface of these materials and are converted into the final catalykically active form by subs~ucnt thermal treatment. The oneness of distribution (dis~ioa) of the catalytieally active particles in the final catalyst, aid thus the catalytic metal surface area available for the catalytic process, depends critically on rlte type of process and method used for these two processes (deposition and thernnal treatment).
A variety of processes has been disclosed for deposition of the catalytically active compon~cats on the powdm~ad support material. These include, for example, impregnation with an excess of impregnation solution. hu this case an aqueous solution of the eatalytically active components is added to the powdorcd support material, when the volume of the solution may he substau'ally greater than the water absorption capacity of the support material. Thus a material is pmdu~cod which has a thick pasty 1 S consistency and which is dewatered, for example, in as oven at elevated tezaperatures of 80 to 150°C. Chromatographic effects may take place durhrg the dewatering of this material which can load to non-uniform distribution of the catalyticahy active components on the support matacial.
For pore volume impregnation, an amount of solvent is used to dissolve the catalytically active components which cozr~ponds to abort ?0 to 110 % of the absorption capacity of the support material for this solvent. The solvent is generally vuater. This solution is distributed as uniformly as possible, for example by spraying over the support material which is being rolled about in a teak. Altar distribution of the entire solution oven tbve support materiel the latter is still frce~-flowing, ddapite the water content. Chromatographic efforts can be largely avoided using pore volume impregnation. This mt~od usually provides better results titan the impregnation process using as excess of solvent described above.
For a proacas for so-called hpmogea~eous deposition from sohttion, the support material is first suspended inn, for example, water. Then an aqueous solution of precursor compounds of the catalyticahy active cod is added using capillary injection with constant stirring. Capillary infection is understood tv be the slow addition of the solution uncle; the surface of the suspension of support material, using a capillary. As fast and as homogeneous a distribution as possible of the prxursor compounds over the entire volume of the suspension is intended to be crnsurad by intensive stinting and slow addition. Here, some adearption of the poor compounds, and thus the fornaationt of crystallisation seeds, takes place at the surface of the support material. The extent of this adsorption depends on the combination of support material acrd precursor compound. With material combinations which do not ensure adequate adsorption of the precursor compounds on the support material, or when chemical fixing of the catalytacally active cxymponents to the support material as desired, the precursor compounds can be precipitated on the support material by capillary injection of a base into the suspension of the support material.
To complete preparation of the catalyst material, the support material coated with the catalytically active components is subjected to a subsequent thermal tnarmant which converts the precursors of the catalytieally active components into the catalytically active form and optionally leads to the foraratian of an alloy Temperatures of more than 300°C up to 1000°C and trcatament times of 0.5 to 3 hours are required for this. Typically, batch processes are used for this in which the catalyst material is agglonnerated and the noble metal particles become coarser due to the long treatme»t times and the siat~ effects which take place. Noble metal particles up to 50 nm or larger eau develop in this way. To form an alloy, temp~auur~ above 900°C and treatrncnt times of at least 0.5 hours are usually required, whcrain there is a risk of excessive particle growth due to sintering.
However, it is iaipo=tant that the catalysts have as higb a surface arcs as possible (i.e. high dispersion) on the support in order to ensure high catalytic activity. Catalysts with average particle sizes for the nobly metals of more them 20 nm are usually not vary active.
Support materials coeted wills catalysts using known ~c~scsj for tneahnent 2S cannot simultaneously comply wills the conflicting requirements for well deveiop~!
crystallinity or alloy structure sad small average particle diameters far the noble metal particles.
In an alternative pmceas for the thermal troatme~nt of powde~rod eubsiances the powdered substances arc traet~ in a high temperahue flow rtactos. The treatmanc temp~atwre is the flow reactor may be higher than 1000°C. Tha time of tre~atma~nt may 6e varied between 0.01 seconds and a few minutes. Finely dispersed noble motels can then be deposited on, for example, aluminium oxide.
rt has also been suggested that a turbulent or laminar burner be used as an eaaandal source of heat. The process is thus performed is an oxidizing aanosphere and is not suitable for preparing catalysts on sttpporc materials made of carbon (graphite, carbon black), such as those used for fuel calls. The carbon black support would be oxidized and some would be burnt away.
Based on the forgoing, there is a need in the art for methods of preparing a noble mewl-containing supported catalysts which have a high txystalliaity ox a well-developed alloy saucture. 'There is also a need for noble metal-containing supported catalysts that have a small particle size and high dispersion.
SUMMARY OF ~~',,J~IY~'I~?N
The present invention provides a noble ~xrrtal-containing supported catalyst which eoataxna ane of the noble mceals from the group Au, Ag, Pt, Pd, Rh, Ru,1r, Os or alloys of one or more of these metals on a powdered support material. The supported catalyst contains particles of noble metal deposited on the support material having a relative degree of crystallinity Cue, determined by ~C-ray diffiaetion, of more than 2, preferably morn than 5, and an average particle size between 2 and 10 nm.
For a bettor understanding of the presort invatdioa together with other and further advantages and enabOdimenta, rats is made to tine Following description taken in eonjut~tion with the examples, the accopc of the which is set forth in the appended claims.
F
The prefaced embodiments of the iaves~tion have been ebosnnt for purposes of illustration and description but are not intended to restrict the scope of the invention in any way, The prefemad embodiments of ceatain affects of the invention era shown in the accompanying figure, wherein:
Figure 1 illustrates an apparatus for thermal tt~ratmesrt of the catalyst precursor to prepare the catalyst of the euxrent invention.
D
The present inveuntion will now be des'Cribed in coninection with pre~d embodiriaents. These embodiments are presented to aid in au understanding of the present invention and are not intended to, and should not be construed, to limit the invention in any way. All alternatives, modifications and equivalents that may become obvious to those of ordinary skill upon reading the disclosure are included within the sprit and ~;ope of the present invtntian, This disclosure is not a primer on pring noble matal-containing supportcd catalysts, basic concepts known to those skilled in the art hava not been set forth in detail.
'1"he catalyst according to the invcntion, due to the thermal treatment which is described below, has a very high crystallinity, filae relative degrec of cxystallinity Cx, which cats be determined by radiographic measurements, was introduced by the inventors for the Quantitative determination of crystallinity: It is de8»ed by equation (1):
~x ~~ (1) I, The rclative degree of cryatalliaity is dete3mined by radiagsnphic measurements on powdered sanaplea (powder diffractomcter from the Stoe Co., copper Kcc radiation). rn equation ( 1 ) Ix rcprescnts the intensity of a specific diffraction reflex (measured in counts) from the catalyst sample. rn the case of platinum, for example, the (hkl 111 reflcx is ~, which can be regarded as a measure of high electrochemical activity for the reduction of oxygen. l, is the intetwity of x-ray diffraction from an K'ra~
amorphous standard with the sauna composition as the catalyst sample, wherein the inta~sity of the X-ray diffraction reflex from the sample is determined at the same angle as for the sample. Itt the case of a carbon supported platinum sample, the amorphous standard is a material with a particle size for the platinum of less than 2 um which no longer exht'bits any X-ray diffraction retlaxcs.
Dc~nding on the intended application of the catalyst, different support matcrials can be used. For use as anode or cathode catalysts in fuel cells, electrically cosxductive support materials basal on carbon from the group carbon black, graphite, active carbon and fibrous, graphitic nertotubes arc normally used. For car cxhaust gas catalysts, on the other hand, oxidic materials from the group of active aluminium oxide, aluminium silicate, zoolitc, titanium oxide, zirconium oxide, rare earth oxides or mixtures or mixed oxides thexeaf are used. Furthermorc, the noblc metals in the catalyst may also be alloyed with at least one bast metal fraxu the group Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu and Zen. These base metals act as promoters, that is they nnodif~
the catalytic effect of the noble metal.
'The cataiysc according to the invention is particularly preferably suitable for use as an anode or cathode catalyst in fbel cells. As a cathode catalyst it has, for example, platinum on carbon black in a concaatration between 5 and 80 wt %, with respect to the total weight of support material and platinum. As an anode catalyst, an the other hand, a CO-tolerant PtlRu alloy on carbon black in a conccntiradon 5 and 80 wt.°~6, with respect to the total weight of support matmial cad alloy, is used, wherein the atomic ratio of Pt to Ru is between 5:1 and 1:5. The support material, carbon black, intended for these applications has a surface area of at least 40 m2/g.
An essential feature of flue catalyst acemdistg to the invention is that the requirements for degree of crystallimity and for particle size arc satisfiat simultaneously. It than exhibfts superior properties when used as a catalyst in fuel calls and for exhaust gas treatment for internal combustion engines.
These requi~nonts can be satisfied wlustt the following steps arc taken during preparation. l:'irst, it has to be ensured that deposition of the nobly metal on the support 1 S material is performed in such a way that the noble metal particles being formed era not larger than 10 mn. It was found that this condition can be complied with, for example, using pore volume impregnation or h~awgeaeous deposition from solution. In the case of hoasoganeous deposition from solution, the coated support material is separated from tree solution, dried and optionally subjected to mild calcination, which is performed ins 24 such a way that no substantial inemase in the particle size of the noble motel particles occurs. A precursor of the catalyst which has to be subjected to further ihernaal treatanent is order to increase the crystallinity and optionally for alloy production is obtained in this way. In the case of pore volume impregnation, the impregnated material can be used directly as a precursor for further thermal traatmterrt without additional 25 drying and calcination steps.
Subsequent thermal treatrnent of the prewraor of the catslyat meat ensure that the roduirernents relati~ to relative degree of aystallinity and average particle size are complied with. It was found that this is possible when the precursor of the catalyst is subjected to a brief thermal trcatraent at temperatures between 1000 axed 1800 °C for a 30 period of loss than one minute.
The heat energy reduired for 1 treatment should fly be transferred to the support material by radiation. 'This procedure caablea rapid heating of the particles in the support matariaY. Radiation heating is particularly prc~err~ed in the case of carbon-containing support rcaaterials such as, for exarrrple, carbon black or active b f carbon. These materials absorb the itxident heat radiation almost completely and thus heat up parhicularly rapidly.
TO perform thermal traatinatzt of the support materlat, it is fast continuously dispcrsad 1n an rnert earner gas heated t0 a teanperahua batv~~s 300 and S00°C.
S Preheating the carrier gas has to be restricted to a tempamhue at which no substantial incceasa in the size of the noble metal particles takes piece. Then the gas stream is passed through a reaction tube. The tamparatuc~ of the tube wall is maintained at the desired treatment temptraturc of 1000 to 1800°C by an e~trmal heating syst~n. The volutrtc flow of the carrier gas is chvsan so thax the duration of passage through the reaction tuba is in the ratrge from a few seconds up to at most one minute.
This rcsidenca time is Rapt short so fbat the actual heating of the support materiel takes place as a result of the transfer of radiated heat and only to a small extcat by thermal conduction from the tuba wall via the camieAr gas. Suitably residence tixrtes, also called treatment times in the following, may amount up to 1 minute, but prceferabay arc 1 S selected betw~n, 0.1 and 20 seconds and most preferably between 0.S and 10 seconds.
Heating of the particles of support materisi by tl~e supply of radiated heat takes place substantially more rapidly then would be posar'ble by the rt of heat tht~ough the carrier gas. ARer leaving the reaction tube, the support mst~al and carrier gas are cooled rapidly to a t~ampm~alum below about 500°C in order to prevent excessive crystallite growth. Afterwards, the catalyst nnnterial prepared in this way is separated from the carrier gas stream and taken for subsequent use.
Duo to the very sudden heating up to the teestmeat temperature of the catalyst precursor followed by cooling agar only a very short treatment time, it is ensured that good ctystallinity or alloy structure can develop within the noble metal particles, but 2S excessive particle growth due to di~tsion on the siufa<x of the support material is suppressed. Tha short tteatxnant times mean that the use of gubstantiaUy high~x treatment tmnperatures than those used for conventional ealcination is possible. The high treatment ttures act in am advantageous manner on the speed with which the crystal structure of the noble metal particles is dcvelopal.
The figure shows the main layout of a poss~le apparatus for themaal treamacnt of the catalyst precursor in order to prepare a catalyst in accordance with tic invcation.
The catalyst precursor is the starting material (1) and is supplied continuously to a gas dispcrser (2). To disperse the powdered startiuag malarial, the dispcrsar is provided with any inert dispersing gas (3), generally nitrvgan. After leaving the dispGraer, the dispersing gas loaded with starting material is admixed with a eo-csUed earriar gas (6) which has been heated in heating unit ('i~, before the mixing process, to art extent such that the ttw~e of the solidsJgas dispersiaa aRer mixing is between about 350 and 500°C. At this tturo, the solidsJgas dispersion mrters a reaction tube (4) which is S heated from outside by a heating device (5) to the desired treatment temperature between 1000 and 1800°C. °fhe volume flow of the eanrier gas added is such that the desired treatmatt tirtse fox the starting material is obtained inside the reaction tube, taking into account the dimensions of the reaction tube. After leaving the inaction tube, the carrier gas stream and the stsxtiag material enttr a rapid cooling unit (8) in which the treated starting material is very rapidly cooled to a tonoperaturo of loss than about 500°C by blowit~ in, far example, nttmgen (9). Finally, in tlae filter unit (10), the final catalyst material is separated form the carrier gas and is discharged as product (11).
Due to the short residence time of the starting m$terial in the reaction tube, there is only a small transfer of heat due to thermal conduction via the gas phase.
Rather, the starting material is manly heated very rapidly by radiated heat from the wall of the reaetiost tube acrd accordingly can also be cooled again very rapidly. To avoid the introduction of air, a syght overpressvre is maintained inside the entire apparatus.
As a rexult of the short-term thermal troatmoat described, the particle sizes of the noble metal particles are enlarged only very slightly. pue to thermal treatmcat in conven'onal rotary kilns, or batchwise in chamber kilns, suet short aeat~ment times as those achieved with the ~pa~ratus described cannot be realised. In addition, in comparison W conventional thermal treatments in which the goods to be treated arc introduced is dishes, vats or other containers. thierie is substantially less agglomeraaoa and caking of the eata[yst material. This is achieved by dispasiag the catalyst in a continuous stream of carrier gas.
Catalysts according to the invention have only small average panicle sues of less than 15 rein, preferably lees tbart 10 rein, due to the special thermal treatanent process. Their specific metal $urff~a aura is nn the range 20 to 200 rn~/g, At the same time, they have a high crystalli»ity. As shown by determining the relative degree of crysmllinity Cx defined above, this is a factor of 2, and in ga~al even a feeler of 5, greater than the relative degrc;e of crystalliniry of traditional catalysts.
A preferred area of application of the catalyst according to the invention its its use as anode or cathode catalyst in fuel ceps. In PEM fuel cells (polymer electrolyte membrane foal cells), platinum and plati»um alloys on a conductive auppo~t material (mostly carbon black or graphite) are used as anode and cathode catalyst. The ccaneentration of noble metal is between 10 and 80 wt.%, with raapdct to the total weight of catalyst.
For the anode aide of PEM fuel calls (polymer electrolyte membrane fuel colla), carbon black supported platizrum/rutb.~ium catalysts are genearalty used. The ratio platinum/ruthenium is in the range Pt/Ru ~ 5:1 to 1:5 (atomic ratio), wherein the ruthenium, in an aleetrochamical Redox reaction with water (,.spill over effect', reduces CO-poisoning of the platinum catalyst. Carbon monoxide-containing hydrogen mixtures are used in tlu case of refonnato-operated titel cells.
PtRu elecorocatalysts have long been known in the p~tior art ielatng to this area.
To condition the materials far PtRu electrocatatysts, costly batch processes arc used in which the sixc of tbc catalyst particles is inracased.
For the cathode side of PEM fuel calls, pure Pt cataly$ts with a Pt loadiag of to 80 wt% are preferably used. However, allays of platinum with base metals (8M) such as chromium, tungstea, nickel, copper or cx~balt arc also used. The amounts added here are ganaahy in the range PtBM ~ S:1 to 1:5 (atomic ratio).
With an anode catalyst aecordiog to the inveptiort, based on PtRu/C, the high crystallinity brings about reduced adsorption of carbon monoxide on the crystallite surface and thus a reduced tendency to be poisoned. The catalyst thus has a higher tolerance towards carbon nsonoxide.
On the cathode side of foal cells, ovhere pros platinum catalysts are used, the activity of the catalyst for oxygen reduction reaction (ORR) is datermi~d by the number of crystallite planes is the platinum crystal. rn order to incroast the activity of Pt electmcatalysts, charefore, it is insufficient simply to maxitniae the Pt surface area.
Rather, it is n~ssary to achieve high crysdsllinity with large Pt atuface areas in order to maximise the fraction of (100), (110) and (111) platinum surface atoms is pnoportiott to this total nwmber of pladnnim atoms. This requirerncut is complied with in an ideal ma»ner by the catalyst according to the invention. Thorefone it is especially suitable for use in low-t~rnpe~ature foal cells (PEMFC, DMFC, PAFC)_ Having now generally deseribod the invention, the same may be more readily understood thmugh the following ~ to the following examples, which are provided by way of illustration and arc not intended to limit the pteso~rt invention unless specified.
i ~3sb E~A~PLES
The following pies are intendat to explain the invention further.
S Two kilograms of a carbon black supported electrocatalyst (noble metal loading 26.4 wt,% platinum acrd 13.6 wt.% ruthenium as Vulcan XC 72, atomic redo Pt : Ru = 1:1, prepared ins accordance with US 6,007,934) are mate~rerl into a gas dispersar using a dosing balance acrd fuaely distributed with tutrogcn as dispersing $as.
The catalyst is than transported into the reaction tuba in a stream of z~itrogea preheated to 350°C.
Process parameters:
Carrier gas: nitrogen Amount of carrirn gas: 8 m'/hour (nitrogen) Temperature (carrier 350C
gas):
Treat<ritcnt temperature:i 300C
Treatment time: 3 s (spprox) Amount metered in: 1100 g /!tour The treated catalyst is doled with nittngea is the rapid cooling emit and collected in the filter unit. A process control systarrt is nsad to adjust the parameters and to monitor the lama.
The catalyst frosted in this way has the following pmparbies:
Radiographic measurcmants (reflection hkl 111, 2 Theta ca 40°):
Particle size (XRD): 6.3 am Lattice constant: 0.3852 wn Intensity (Ix, XRD):2800 counts IntCt1$ity (1D, ~) 400 COtlatS
De~ee of crystallinity 6 Cx:
For comparison, the untreated starting material has the following data:
Particle si~zc(XRD): 2.6 rnn Lattice constant: 0.3919 nna Intensity (I%, X'1tD): 800 counts Intensity (I,, XItD) 400 counts Degree of crystallinity1 Cx:
Due to the high ccystallinity and, at the same time, small particle size, the treated electroeatalySt exln'bits very good electrical p~rop~ties in a PfiM
fuel cell, in fact as an anode catalyst under bath hydroganlair an;d also reformatrJair operation.
100 grams of the carbon black-supported electrocatalyst (noble metal loading 26.4 wt % platinum and 13.6 vvt.°lo nitheniuin on Vulcan XC ?2, atomic ratio Pt : Ru 1:1, cornpsre with example 1) are treated at 850°C for 60 min undo nitrogen in a conventional batch process. After thermal tteat~naent in the kiln the material is allowed to cool under a protective gas.
Properties:
Particle size (XRD): 13.6 ntn Lattice constant: 0.3844 nm Intensity (Ix, XRD): 1300 counts Intensity (1" XItD) 400 counts Degree of erystallirxity2.25 Cx:
In direct contrast to acample 1, the catalyst has a lower perforanance in PEM
fuel cells due to the hig)a particle size of 13.6 am.
1335b One kilogram of a carbon black-supported electrocatalyst (platiusunn loading wt.°~ on 'Vulcan XC 72) is minto a gas dispearsa~r using a dosing balance and finely distributed with rtitrogat as the iaqjector gas strum. The catalyst is then S transported into the inaction tube in a stream of nitrogen preheated to 350°C.Process parameters:
Carrier gas: nitrogen Amount of carrier gas; $ m'/hour (nitrogen) Ternpaatirre (carrier 350C
gas):
Treatment tempErature:1200C
Treatment lima: 3 s (approx) Amount rttetercd in: 1000 g /hour The gated catalyst is cooled with nitrogen is the rapid cooling unit and ~ileoted in the filter unit. A process control system is used to adjust the parameters and to monitor the same.
The catalyst treated in this way has the following properties:
Particle saza (7~RD): 6.5 nm Lattice constaixt: 0.3931 not Intensity (I,~, XItD): 3000 counts Intronsity (I" XRD) 400 counts Degree of crystallinity6.S
Cx:
Far comparison the untr~d starting xnataial has the following data:
Particle six (XRD): 3.9 nm Lattice constant: 0.3937run as Intensify (I", XRD):1640 counts Intensity (I, X1ZD) 400 counts Degrre of arystallinity3 C":
Due to the high degxeo of cryxulliniry and, at the same tir:rte, small particle sire, the aoatad alCC~catalysc mchibits very good clactrical p~rope~es in a PFM fuel coal, in fact in particular as a cathode catalyst under itydrogar/air operation.
i3ss6 One kilogram of a carbon black-aapported ele~aatalyst (platimu» content 40 wt.% on Vulcan ACC 72, atomic redo Pt:Cr = 3:1 ) arc mebcred into a gas disperser using a dosing balance and finol~r distributed with nitrogen as dispersing gas. The catalyst is then darted into the reaction tubo in a stream of nitrogen pmheatcd to 350°C.
Process parameters:
Carciar gas: nitrogen Amount of carrier gns: 8 m'llioux (nitmgon) Temperature (carrier 350C
gas):
Treatment temperature:100C
Treatment time: 3 s (approx) Amount metered in: 1000 g /hour The treated catalyst is cooled with nitrogen in the rapid cooling wait and collated in the filter unit. A process control systeucn is used to adjust the parameters arid to monitor tho same.
The catalyst trued in this way has the following ~opcrties:
ltadiograpbic measurements (reflection hhl 1 l 1, 2 These ca. 40°):
Particle size (XR.D): 7.S stn lattice constant: 0.385 ~
Intensity (I,~, XRD):3200 counts Tntensity (In, ACRD) 400 counts Degree of aystallinity 7 Cx:
Dae to the high degree of crystallinifiy and, at the same time, small particle size, the treated electrocatalyst exhibits very good electrical prope~rihi~ in a PEM
fuel cell, in fact in particular as a cathodo catalyst under hydroganJair operation.
rotmpof i~aw, 2: Pt~r/ rvi 4 coav_.~..~..e. trg~~
100 grams of a carbon black-supported electrocatalyst (platinum content 40 ~wt.% platinum on Vulcan XC 72, atomic ratio Pt : Cr = 3: I, compare with example 3) are treated under forming gas at 900°C for 60 min in a conventional batch process.
i335b Afta~ thermal treat~meut in the Idln, the naate~i~al is alloyed to cool tusdex s protective gas.
Properties:
Particle size (XRD): 16 nm Lattice coa~nt: 0.386 noon Intensity (Ix, XRn): 2000 comats Intensity (In, ~ItD) 400 counts Degr~ of crystallinity 4 Cx:
In direct comparison to example 4, the catalyst, has a low performance in PEM
fttel acUs duc to the high particle size of 16 nm.
Ca. 2 kg of a rnoiat powder, proparnd by pore volume imprcgnatian of the support with the noble metal solution (incipient wetnass method) consisting oI' 78 wr.% alumiruitua oxide (y-A1Z03. BET surface area 140 mz/g) 20 wt.% water 2 wt.°!o platinum nitrate arc mcterad into the gas diapex~sac using a dosing balance, finely distributed with nitrogen as dispezeing gas and tra~partcd into tha reaction tube, Process parameters:
Carrier gas: nitrogen Amount of carrier gas: 8 m3lb~our (nitrogrn) TempeTatura (carrier 350C
gas):
Treatment temperature: 1100C
Treatme>zt time: 3 s (approx) Amount metered in: 1000 g ltwur After leavit~ the reaction tube, the treated aat~rst is cooled with nitrogen in the rapid cooling unit and collected in the filter unit. A process control system is used to adjust the parsmatrrs and to monitor the same.
The catalyst treatod in this way has the following pmpatses:
Composition: 2.5 wt.% Pt on aluminium oxide Particle size (XRD): 5 nm late~nsity(1~, XRD): 3400 cou~ats Intensity (I,, XRD) 400 counts Degree of crystallinity Cx: 7.s The catalyst in a conventional process (900°C, residence time b0 min, riitrogcn), on the other hand, has a particle size of 12 ~ aad a degree of crystallinity ~C,~ ~ 4.
The catalyst from example 4 is used is gas p~haae catalysis, for example as a catalyst for the areatment of exliaust gasps fmm inta~nal combustion engines or as a catalyst for tile selective oxidation of CO in so-called PROX reactors for tire pucificataon of hydrogen in foal cell systems.
Due to t'hc~ axnall particle size and, at tlu; soma time, high crystallinily, very good results sre obtaiaed, in psrtieular for the working lifddurability of the catalyst.
'While the invention has beeai described in connection with specific embodiments thereof, it will be wa~de~stood that it is capablo of modifications sad this application is intended to cover any variations, uses, or adaptations of the invention followitag, in general, the principles of the i~tvar~tion and including such dfrom the present disclosure as come within lrnown or customary practice within the art to which the invention pertains sad as may be applied to ~e essential features hercinbefora sat forth and ca follows in the scope of the appended claims.
is
An essential feature of flue catalyst acemdistg to the invention is that the requirements for degree of crystallimity and for particle size arc satisfiat simultaneously. It than exhibfts superior properties when used as a catalyst in fuel calls and for exhaust gas treatment for internal combustion engines.
These requi~nonts can be satisfied wlustt the following steps arc taken during preparation. l:'irst, it has to be ensured that deposition of the nobly metal on the support 1 S material is performed in such a way that the noble metal particles being formed era not larger than 10 mn. It was found that this condition can be complied with, for example, using pore volume impregnation or h~awgeaeous deposition from solution. In the case of hoasoganeous deposition from solution, the coated support material is separated from tree solution, dried and optionally subjected to mild calcination, which is performed ins 24 such a way that no substantial inemase in the particle size of the noble motel particles occurs. A precursor of the catalyst which has to be subjected to further ihernaal treatanent is order to increase the crystallinity and optionally for alloy production is obtained in this way. In the case of pore volume impregnation, the impregnated material can be used directly as a precursor for further thermal traatmterrt without additional 25 drying and calcination steps.
Subsequent thermal treatrnent of the prewraor of the catslyat meat ensure that the roduirernents relati~ to relative degree of aystallinity and average particle size are complied with. It was found that this is possible when the precursor of the catalyst is subjected to a brief thermal trcatraent at temperatures between 1000 axed 1800 °C for a 30 period of loss than one minute.
The heat energy reduired for 1 treatment should fly be transferred to the support material by radiation. 'This procedure caablea rapid heating of the particles in the support matariaY. Radiation heating is particularly prc~err~ed in the case of carbon-containing support rcaaterials such as, for exarrrple, carbon black or active b f carbon. These materials absorb the itxident heat radiation almost completely and thus heat up parhicularly rapidly.
TO perform thermal traatinatzt of the support materlat, it is fast continuously dispcrsad 1n an rnert earner gas heated t0 a teanperahua batv~~s 300 and S00°C.
S Preheating the carrier gas has to be restricted to a tempamhue at which no substantial incceasa in the size of the noble metal particles takes piece. Then the gas stream is passed through a reaction tube. The tamparatuc~ of the tube wall is maintained at the desired treatment temptraturc of 1000 to 1800°C by an e~trmal heating syst~n. The volutrtc flow of the carrier gas is chvsan so thax the duration of passage through the reaction tuba is in the ratrge from a few seconds up to at most one minute.
This rcsidenca time is Rapt short so fbat the actual heating of the support materiel takes place as a result of the transfer of radiated heat and only to a small extcat by thermal conduction from the tuba wall via the camieAr gas. Suitably residence tixrtes, also called treatment times in the following, may amount up to 1 minute, but prceferabay arc 1 S selected betw~n, 0.1 and 20 seconds and most preferably between 0.S and 10 seconds.
Heating of the particles of support materisi by tl~e supply of radiated heat takes place substantially more rapidly then would be posar'ble by the rt of heat tht~ough the carrier gas. ARer leaving the reaction tube, the support mst~al and carrier gas are cooled rapidly to a t~ampm~alum below about 500°C in order to prevent excessive crystallite growth. Afterwards, the catalyst nnnterial prepared in this way is separated from the carrier gas stream and taken for subsequent use.
Duo to the very sudden heating up to the teestmeat temperature of the catalyst precursor followed by cooling agar only a very short treatment time, it is ensured that good ctystallinity or alloy structure can develop within the noble metal particles, but 2S excessive particle growth due to di~tsion on the siufa<x of the support material is suppressed. Tha short tteatxnant times mean that the use of gubstantiaUy high~x treatment tmnperatures than those used for conventional ealcination is possible. The high treatment ttures act in am advantageous manner on the speed with which the crystal structure of the noble metal particles is dcvelopal.
The figure shows the main layout of a poss~le apparatus for themaal treamacnt of the catalyst precursor in order to prepare a catalyst in accordance with tic invcation.
The catalyst precursor is the starting material (1) and is supplied continuously to a gas dispcrser (2). To disperse the powdered startiuag malarial, the dispcrsar is provided with any inert dispersing gas (3), generally nitrvgan. After leaving the dispGraer, the dispersing gas loaded with starting material is admixed with a eo-csUed earriar gas (6) which has been heated in heating unit ('i~, before the mixing process, to art extent such that the ttw~e of the solidsJgas dispersiaa aRer mixing is between about 350 and 500°C. At this tturo, the solidsJgas dispersion mrters a reaction tube (4) which is S heated from outside by a heating device (5) to the desired treatment temperature between 1000 and 1800°C. °fhe volume flow of the eanrier gas added is such that the desired treatmatt tirtse fox the starting material is obtained inside the reaction tube, taking into account the dimensions of the reaction tube. After leaving the inaction tube, the carrier gas stream and the stsxtiag material enttr a rapid cooling unit (8) in which the treated starting material is very rapidly cooled to a tonoperaturo of loss than about 500°C by blowit~ in, far example, nttmgen (9). Finally, in tlae filter unit (10), the final catalyst material is separated form the carrier gas and is discharged as product (11).
Due to the short residence time of the starting m$terial in the reaction tube, there is only a small transfer of heat due to thermal conduction via the gas phase.
Rather, the starting material is manly heated very rapidly by radiated heat from the wall of the reaetiost tube acrd accordingly can also be cooled again very rapidly. To avoid the introduction of air, a syght overpressvre is maintained inside the entire apparatus.
As a rexult of the short-term thermal troatmoat described, the particle sizes of the noble metal particles are enlarged only very slightly. pue to thermal treatmcat in conven'onal rotary kilns, or batchwise in chamber kilns, suet short aeat~ment times as those achieved with the ~pa~ratus described cannot be realised. In addition, in comparison W conventional thermal treatments in which the goods to be treated arc introduced is dishes, vats or other containers. thierie is substantially less agglomeraaoa and caking of the eata[yst material. This is achieved by dispasiag the catalyst in a continuous stream of carrier gas.
Catalysts according to the invention have only small average panicle sues of less than 15 rein, preferably lees tbart 10 rein, due to the special thermal treatanent process. Their specific metal $urff~a aura is nn the range 20 to 200 rn~/g, At the same time, they have a high crystalli»ity. As shown by determining the relative degree of crysmllinity Cx defined above, this is a factor of 2, and in ga~al even a feeler of 5, greater than the relative degrc;e of crystalliniry of traditional catalysts.
A preferred area of application of the catalyst according to the invention its its use as anode or cathode catalyst in fuel ceps. In PEM fuel cells (polymer electrolyte membrane foal cells), platinum and plati»um alloys on a conductive auppo~t material (mostly carbon black or graphite) are used as anode and cathode catalyst. The ccaneentration of noble metal is between 10 and 80 wt.%, with raapdct to the total weight of catalyst.
For the anode aide of PEM fuel calls (polymer electrolyte membrane fuel colla), carbon black supported platizrum/rutb.~ium catalysts are genearalty used. The ratio platinum/ruthenium is in the range Pt/Ru ~ 5:1 to 1:5 (atomic ratio), wherein the ruthenium, in an aleetrochamical Redox reaction with water (,.spill over effect', reduces CO-poisoning of the platinum catalyst. Carbon monoxide-containing hydrogen mixtures are used in tlu case of refonnato-operated titel cells.
PtRu elecorocatalysts have long been known in the p~tior art ielatng to this area.
To condition the materials far PtRu electrocatatysts, costly batch processes arc used in which the sixc of tbc catalyst particles is inracased.
For the cathode side of PEM fuel calls, pure Pt cataly$ts with a Pt loadiag of to 80 wt% are preferably used. However, allays of platinum with base metals (8M) such as chromium, tungstea, nickel, copper or cx~balt arc also used. The amounts added here are ganaahy in the range PtBM ~ S:1 to 1:5 (atomic ratio).
With an anode catalyst aecordiog to the inveptiort, based on PtRu/C, the high crystallinity brings about reduced adsorption of carbon monoxide on the crystallite surface and thus a reduced tendency to be poisoned. The catalyst thus has a higher tolerance towards carbon nsonoxide.
On the cathode side of foal cells, ovhere pros platinum catalysts are used, the activity of the catalyst for oxygen reduction reaction (ORR) is datermi~d by the number of crystallite planes is the platinum crystal. rn order to incroast the activity of Pt electmcatalysts, charefore, it is insufficient simply to maxitniae the Pt surface area.
Rather, it is n~ssary to achieve high crysdsllinity with large Pt atuface areas in order to maximise the fraction of (100), (110) and (111) platinum surface atoms is pnoportiott to this total nwmber of pladnnim atoms. This requirerncut is complied with in an ideal ma»ner by the catalyst according to the invention. Thorefone it is especially suitable for use in low-t~rnpe~ature foal cells (PEMFC, DMFC, PAFC)_ Having now generally deseribod the invention, the same may be more readily understood thmugh the following ~ to the following examples, which are provided by way of illustration and arc not intended to limit the pteso~rt invention unless specified.
i ~3sb E~A~PLES
The following pies are intendat to explain the invention further.
S Two kilograms of a carbon black supported electrocatalyst (noble metal loading 26.4 wt,% platinum acrd 13.6 wt.% ruthenium as Vulcan XC 72, atomic redo Pt : Ru = 1:1, prepared ins accordance with US 6,007,934) are mate~rerl into a gas dispersar using a dosing balance acrd fuaely distributed with tutrogcn as dispersing $as.
The catalyst is than transported into the reaction tuba in a stream of z~itrogea preheated to 350°C.
Process parameters:
Carrier gas: nitrogen Amount of carrirn gas: 8 m'/hour (nitrogen) Temperature (carrier 350C
gas):
Treat<ritcnt temperature:i 300C
Treatment time: 3 s (spprox) Amount metered in: 1100 g /!tour The treated catalyst is doled with nittngea is the rapid cooling emit and collected in the filter unit. A process control systarrt is nsad to adjust the parameters and to monitor the lama.
The catalyst frosted in this way has the following pmparbies:
Radiographic measurcmants (reflection hkl 111, 2 Theta ca 40°):
Particle size (XRD): 6.3 am Lattice constant: 0.3852 wn Intensity (Ix, XRD):2800 counts IntCt1$ity (1D, ~) 400 COtlatS
De~ee of crystallinity 6 Cx:
For comparison, the untreated starting material has the following data:
Particle si~zc(XRD): 2.6 rnn Lattice constant: 0.3919 nna Intensity (I%, X'1tD): 800 counts Intensity (I,, XItD) 400 counts Degree of crystallinity1 Cx:
Due to the high ccystallinity and, at the same time, small particle size, the treated electroeatalySt exln'bits very good electrical p~rop~ties in a PfiM
fuel cell, in fact as an anode catalyst under bath hydroganlair an;d also reformatrJair operation.
100 grams of the carbon black-supported electrocatalyst (noble metal loading 26.4 wt % platinum and 13.6 vvt.°lo nitheniuin on Vulcan XC ?2, atomic ratio Pt : Ru 1:1, cornpsre with example 1) are treated at 850°C for 60 min undo nitrogen in a conventional batch process. After thermal tteat~naent in the kiln the material is allowed to cool under a protective gas.
Properties:
Particle size (XRD): 13.6 ntn Lattice constant: 0.3844 nm Intensity (Ix, XRD): 1300 counts Intensity (1" XItD) 400 counts Degree of erystallirxity2.25 Cx:
In direct contrast to acample 1, the catalyst has a lower perforanance in PEM
fuel cells due to the hig)a particle size of 13.6 am.
1335b One kilogram of a carbon black-supported electrocatalyst (platiusunn loading wt.°~ on 'Vulcan XC 72) is minto a gas dispearsa~r using a dosing balance and finely distributed with rtitrogat as the iaqjector gas strum. The catalyst is then S transported into the inaction tube in a stream of nitrogen preheated to 350°C.Process parameters:
Carrier gas: nitrogen Amount of carrier gas; $ m'/hour (nitrogen) Ternpaatirre (carrier 350C
gas):
Treatment tempErature:1200C
Treatment lima: 3 s (approx) Amount rttetercd in: 1000 g /hour The gated catalyst is cooled with nitrogen is the rapid cooling unit and ~ileoted in the filter unit. A process control system is used to adjust the parameters and to monitor the same.
The catalyst treated in this way has the following properties:
Particle saza (7~RD): 6.5 nm Lattice constaixt: 0.3931 not Intensity (I,~, XItD): 3000 counts Intronsity (I" XRD) 400 counts Degree of crystallinity6.S
Cx:
Far comparison the untr~d starting xnataial has the following data:
Particle six (XRD): 3.9 nm Lattice constant: 0.3937run as Intensify (I", XRD):1640 counts Intensity (I, X1ZD) 400 counts Degrre of arystallinity3 C":
Due to the high degxeo of cryxulliniry and, at the same tir:rte, small particle sire, the aoatad alCC~catalysc mchibits very good clactrical p~rope~es in a PFM fuel coal, in fact in particular as a cathode catalyst under itydrogar/air operation.
i3ss6 One kilogram of a carbon black-aapported ele~aatalyst (platimu» content 40 wt.% on Vulcan ACC 72, atomic redo Pt:Cr = 3:1 ) arc mebcred into a gas disperser using a dosing balance and finol~r distributed with nitrogen as dispersing gas. The catalyst is then darted into the reaction tubo in a stream of nitrogen pmheatcd to 350°C.
Process parameters:
Carciar gas: nitrogen Amount of carrier gns: 8 m'llioux (nitmgon) Temperature (carrier 350C
gas):
Treatment temperature:100C
Treatment time: 3 s (approx) Amount metered in: 1000 g /hour The treated catalyst is cooled with nitrogen in the rapid cooling wait and collated in the filter unit. A process control systeucn is used to adjust the parameters arid to monitor tho same.
The catalyst trued in this way has the following ~opcrties:
ltadiograpbic measurements (reflection hhl 1 l 1, 2 These ca. 40°):
Particle size (XR.D): 7.S stn lattice constant: 0.385 ~
Intensity (I,~, XRD):3200 counts Tntensity (In, ACRD) 400 counts Degree of aystallinity 7 Cx:
Dae to the high degree of crystallinifiy and, at the same time, small particle size, the treated electrocatalyst exhibits very good electrical prope~rihi~ in a PEM
fuel cell, in fact in particular as a cathodo catalyst under hydroganJair operation.
rotmpof i~aw, 2: Pt~r/ rvi 4 coav_.~..~..e. trg~~
100 grams of a carbon black-supported electrocatalyst (platinum content 40 ~wt.% platinum on Vulcan XC 72, atomic ratio Pt : Cr = 3: I, compare with example 3) are treated under forming gas at 900°C for 60 min in a conventional batch process.
i335b Afta~ thermal treat~meut in the Idln, the naate~i~al is alloyed to cool tusdex s protective gas.
Properties:
Particle size (XRD): 16 nm Lattice coa~nt: 0.386 noon Intensity (Ix, XRn): 2000 comats Intensity (In, ~ItD) 400 counts Degr~ of crystallinity 4 Cx:
In direct comparison to example 4, the catalyst, has a low performance in PEM
fttel acUs duc to the high particle size of 16 nm.
Ca. 2 kg of a rnoiat powder, proparnd by pore volume imprcgnatian of the support with the noble metal solution (incipient wetnass method) consisting oI' 78 wr.% alumiruitua oxide (y-A1Z03. BET surface area 140 mz/g) 20 wt.% water 2 wt.°!o platinum nitrate arc mcterad into the gas diapex~sac using a dosing balance, finely distributed with nitrogen as dispezeing gas and tra~partcd into tha reaction tube, Process parameters:
Carrier gas: nitrogen Amount of carrier gas: 8 m3lb~our (nitrogrn) TempeTatura (carrier 350C
gas):
Treatment temperature: 1100C
Treatme>zt time: 3 s (approx) Amount metered in: 1000 g ltwur After leavit~ the reaction tube, the treated aat~rst is cooled with nitrogen in the rapid cooling unit and collected in the filter unit. A process control system is used to adjust the parsmatrrs and to monitor the same.
The catalyst treatod in this way has the following pmpatses:
Composition: 2.5 wt.% Pt on aluminium oxide Particle size (XRD): 5 nm late~nsity(1~, XRD): 3400 cou~ats Intensity (I,, XRD) 400 counts Degree of crystallinity Cx: 7.s The catalyst in a conventional process (900°C, residence time b0 min, riitrogcn), on the other hand, has a particle size of 12 ~ aad a degree of crystallinity ~C,~ ~ 4.
The catalyst from example 4 is used is gas p~haae catalysis, for example as a catalyst for the areatment of exliaust gasps fmm inta~nal combustion engines or as a catalyst for tile selective oxidation of CO in so-called PROX reactors for tire pucificataon of hydrogen in foal cell systems.
Due to t'hc~ axnall particle size and, at tlu; soma time, high crystallinily, very good results sre obtaiaed, in psrtieular for the working lifddurability of the catalyst.
'While the invention has beeai described in connection with specific embodiments thereof, it will be wa~de~stood that it is capablo of modifications sad this application is intended to cover any variations, uses, or adaptations of the invention followitag, in general, the principles of the i~tvar~tion and including such dfrom the present disclosure as come within lrnown or customary practice within the art to which the invention pertains sad as may be applied to ~e essential features hercinbefora sat forth and ca follows in the scope of the appended claims.
is
Claims (15)
1. A noble metal-containing supported catalyst comprising one or more noble metals selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ru, Ir, Os and alloys thereof deposited in the form of noble metal particles on a powdered support material, wherein the noble metal particles have a relative degree of crystallinity of greater than 2 as determined by X-ray diffraction and an average particle size of between about 2 and about 10 mm.
2. A supported catalyst according to Claim 1, wherein the relative degree of crystallinity as determined by X-ray diffraction is greater than 5.
3. A supported catalyst according to Claim 1, wherein the support material is a carbon-containing material selected from the group consisting of carbon black, graphite, active carbon and fibrous, and graphitic nanotubes.
4. A supported catalyst according to Claim 1, wherein the support material is an oxidic material selected from the group consisting of active aluminium oxide, aluminium silicate, zeolite, titanium oxide, zirconium oxide, rare earth oxides, and mixtures thereof.
5. A supported catalyst according to Claim 3, wherein the noble metals are alloyed with at least one base metal selected from the group consisting of Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
6. A supported catalyst according to Claim 3, wherein the supported catalyst contains Pt on carbon black with a surface area of at least 40 m2/g in a concentration between 5 and 80 wt.% based on the total weight of support material and Pt.
7. A supported catalyst according to Claim 3, wherein the supported catalyst contains a Pt/Ru alloy on carbon black with a surface area of at least 40 m2/g in a concentration between 5 and 80 wt.% based on the total weight of support material and alloy, and wherein the atomic ratio Pt to Ru is between 5:1 and 1:5.
8. A method of using the catalyst according to Claim 1 as an anode or cathode catalyst for a low-temperature fuel cell.
9. A method of using the catalyst according to Claim 1 as a catalyst for the treatment of exhaust gases from an internal combustion engine.
10. A process for preparing a supported catalyst according to Claim 1, comprising providing a support material coated with a precursor of the noble metals using pore volume impregnation; drying the support material; and thermally treating the dried support material at a temperature between 1000 and 1800°C for a period of less than one minute wherein crystallinity and the alloy are developed.
11. A process for preparing a supported catalyst according to Claim 1, comprising providing a support material coated with a precursor of the noble metals using homogeneous deposition from solution; drying the support material;
and thermally treating the dried support material at a temperature between and 1800°C for a period of less than one minute wherein crystallinity and the alloy are developed.
and thermally treating the dried support material at a temperature between and 1800°C for a period of less than one minute wherein crystallinity and the alloy are developed.
12. A process according to Claim 11, wherein heat energy required for thermal treatment is transferred to the support material by radiation.
13. A process according to Claim 11, wherein the support material coated with the noble metal is continuously dispersed in an inert carrier gas stream at a temperature between about 300 and 500°C, passed through a heated reactor and, after leaving the reactor, is rapidly cooled and then separated from the carrier gas stream.
14. A process according to Claim 13, wherein the inert gas stream and support material are cooled to a temperature below 500°C by admixing an inert and cooled gas or mixture of gases with the carrier gas stream.
15. A process for preparing a supported catalyst according to Claim 1 comprising providing a precursor of the supported catalyst, the precursor having one or more catalytically active noble metals with an average particle sizes between 1 and nm on a surface of the support material and thermally treating the precursor at a temperature between about 1000 and 1800°C for a period of less than one minute.
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US6686308B2 (en) * | 2001-12-03 | 2004-02-03 | 3M Innovative Properties Company | Supported nanoparticle catalyst |
JP2003308849A (en) | 2002-04-12 | 2003-10-31 | Tanaka Kikinzoku Kogyo Kk | Catalyst for fuel electrode of high polymer solid electrolyte fuel cell |
JP2003331855A (en) * | 2002-05-16 | 2003-11-21 | Tokyo Inst Of Technol | Cathode catalyst for solid polymer fuel cell and solid polymer fuel cell |
US20040013935A1 (en) * | 2002-07-19 | 2004-01-22 | Siyu Ye | Anode catalyst compositions for a voltage reversal tolerant fuel cell |
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- 2002-05-06 BR BR0201611-7A patent/BR0201611A/en not_active Application Discontinuation
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JP2007289960A (en) | 2007-11-08 |
DE60205061T2 (en) | 2006-04-20 |
JP2003024798A (en) | 2003-01-28 |
JP4125038B2 (en) | 2008-07-23 |
BR0201611A (en) | 2003-03-11 |
KR20020084825A (en) | 2002-11-11 |
US20030045425A1 (en) | 2003-03-06 |
JP4649447B2 (en) | 2011-03-09 |
US20050101481A1 (en) | 2005-05-12 |
EP1254711A1 (en) | 2002-11-06 |
ATE299752T1 (en) | 2005-08-15 |
DE60205061D1 (en) | 2005-08-25 |
US7109145B2 (en) | 2006-09-19 |
US6861387B2 (en) | 2005-03-01 |
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