EP1968742A1 - Auf einem hexaaluminat basierender katalysator für die verbrennung von kohlenwasserstoffen sowie brennstoffzellenanordnung mit abgasbrenner - Google Patents
Auf einem hexaaluminat basierender katalysator für die verbrennung von kohlenwasserstoffen sowie brennstoffzellenanordnung mit abgasbrennerInfo
- Publication number
- EP1968742A1 EP1968742A1 EP06829897A EP06829897A EP1968742A1 EP 1968742 A1 EP1968742 A1 EP 1968742A1 EP 06829897 A EP06829897 A EP 06829897A EP 06829897 A EP06829897 A EP 06829897A EP 1968742 A1 EP1968742 A1 EP 1968742A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hexaaluminate
- fuel cell
- catalyst
- gas
- catalytic burner
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000000446 fuel Substances 0.000 title claims abstract description 67
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 title claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000002245 particle Substances 0.000 claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 29
- 239000002737 fuel gas Substances 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000629 steam reforming Methods 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000006735 deficit Effects 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- 239000000725 suspension Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 238000001354 calcination Methods 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 platinum metals Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QAHFOPIILNICLA-UHFFFAOYSA-N Diphenamid Chemical compound C=1C=CC=CC=1C(C(=O)N(C)C)C1=CC=CC=C1 QAHFOPIILNICLA-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910016583 MnAl Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VMJMQRNRWGOEAE-UHFFFAOYSA-L lithium;potassium;carbonate Chemical compound [Li+].[K+].[O-]C([O-])=O VMJMQRNRWGOEAE-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- H01M4/88—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J35/40—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
- H01M8/04022—Heating by combustion
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
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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
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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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
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/144—Fuel cells with fused electrolytes characterised by the electrolyte material
- H01M8/145—Fuel cells with fused electrolytes characterised by the electrolyte material comprising carbonates
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/2475—Enclosures, casings or containers of fuel cell stacks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0208—Other waste gases from fuel cells
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- B01J37/03—Precipitation; Co-precipitation
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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
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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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
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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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
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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
- Y02P20/10—Process efficiency
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to a process for the preparation of a catalyst for the catalytic combustion of hydrocarbons, in particular methane, a catalyst, as can be obtained with the method, a catalytic burner, and a fuel cell assembly.
- Fuel cells offer the possibility with high efficiency of obtaining electric power from the controlled combustion of hydrogen.
- methanol or hydrocarbons are currently used as a source of hydrogen, from which hydrogen is then produced in an upstream reformer.
- Methanol is liquid under normal conditions and can therefore be transported and stored without major problems.
- Hydrocarbons are also present either under normal conditions liquid form before or they can easily liquefy under pressure.
- natural gas which consists essentially of methane
- an appropriate infrastructure already exists, so that stationary energy aggregates could be operated on the basis of fuel cells with methane as raw material without further notice.
- Methane can be released by steam reforming hydrogen.
- the resulting gas contains traces of unreacted methane and water, essentially hydrogen, carbon dioxide and carbon monoxide.
- This gas can be used as fuel gas for a fuel cell.
- a fuel cell arrangement in which the fuel gas generated from methane and water can be used to generate energy, is described for example in DE 197 43 075 Al.
- Such an arrangement includes a number of fuel cells disposed in a fuel cell stack within a closed protective housing.
- fuel gas is supplied to the fuel cells, which essentially consists of hydrogen, carbon dioxide, carbon monoxide and residues of methane and water.
- the fuel gas is generated in an upstream reformer of methane and water.
- the fuel gas is burned, wherein electrons are generated according to the following reaction equations:
- the anode exhaust gas therefore contains not only the reaction products carbon dioxide and water but also fractions of hydrogen and methane gas.
- the anode exhaust gas is first mixed with air and then fed to a catalytic exhaust gas burner, in which the remaining methane and traces of hydrogen are burned to water and carbon dioxide.
- the released thermal energy is used to heat the carbonate present in molten form in the fuel cell.
- noble metals are used, which are provided on a suitable support in finely divided form.
- the catalytic combustion has the advantage that it is very uniform and without temperature peaks.
- the combustion of palladium catalysts proceeds at temperatures ranging from about 450 to 550 0 C. At higher temperatures beyond about 800-900 0 C, the equilibrium shifts Pd / PdO favor of palladium metal, thereby decreasing the activity of the catalyst. (See Catalysis Today 47 (1999) 29-44)
- the ideal temperature range for operating a fuel cell is in the range of about 600 to 650 ° C.
- the heat produced by the combustion can then be used to recover the fuel gas by steam reforming.
- the completely oxidized anode exhaust gas which in particular no longer contains any hydrogen gas, is fed to the cathode as cathode gas after it leaves the burner.
- the carbon dioxide contained in the cathode gas reacts with the oxygen taking up two electrodes according to the following equation:
- a significant cost in the fuel cell assembly described above is the precious metal catalyst needed for the combustion of the anode exhaust gas. It is therefore endeavored to find catalysts which have a sufficiently high activity at the required temperatures of about 650 0 C and do not include expensive precious metals.
- the catalytic combustion of methane has also been proposed for the power generation of, for example, turbines or other heat sources, although very high temperatures of possibly more than 1000 0 C are generated.
- EP 0 270 203 A1 describes a heat-stable catalyst for the catalytic combustion of, for example, methane.
- the catalyst is based on alkaline earth hexaaluminates which contain fractions of Mn, Co, Fe, Ni, Cu or Cr. These catalysts are characterized by a high activity and resistance even at temperatures of more than 1200 0 C. However, the activity of the catalyst is relatively low at lower temperatures. In order to be able to provide sufficient catalytic activity even at lower temperatures, small amounts of platinum metals are added, for example Pt, Ru, Rh or Pd.
- the catalyst was prepared by the alkoxide process and calcined after precipitation at 1100 0 C.
- the powdery catalyst is kneaded with water and an organic binder and then extruded to a honeycomb structure. After shaping, the catalyst is calcined again at 1200 or 1300 ° C.
- the ceramic catalyst exhibits a relatively high ignition temperature of above 600 ° C.
- the ceramic catalyst is therefore preceded by sections in which a noble metal-containing catalyst is arranged.
- the catalyst system was successfully tested in a 160 kW burner coupled to a gas turbine. During operation of the experimental setup, the temperatures in the catalyst reach values of up to about 1100 ° C.
- the nanocrystals obtained in the hydrolysis are separated from the solvent by lyophilization and then dried under supercritical conditions in order to minimize particle growth of the nanocrystals.
- the nanocrystalline Bariumhexaaluminat shows for methane an ignition temperature of 590 0 C and a complete conversion of methane within a temperature range of 710 to 1300 0 C. By adding cerium, the ignition temperature can be lowered to about 400 0 C.
- the process makes it possible to produce hexaaluminates which show a high catalytic activity during the combustion of methane. For a production of these catalysts on an industrial scale, however, the process is too expensive.
- the combustion of the anode exhaust gas is complete even at low temperatures, so that the waste heat can be used directly for the steam reforming or for the production of the fuel gas.
- the combustion can ideally be controlled so that the waste heat No energy has to be dissipated from the anode exhaust stream to reach the temperatures required for steam reforming.
- a hexaaluminate of the formula MO • 6 Al 2 O 3 is provided in which M is at least one alkaline earth metal, wherein the at least one alkaline earth metal and the aluminum may also be proportionally replaced by one or more other metals, - and
- the hexaaluminate is ground to an average particle size D 50 of less than 3 ⁇ m.
- the hexaaluminate can first be prepared in any desired manner. It is not necessary that the hexaaluminate is obtained in nano- or microcrystalline form.
- the hexaaluminate can be washed and dried in the usual way. If the hexaaluminate is obtained in the form of larger agglomerates, it can first be coarsely crushed.
- the agglomerates can have a very high hardness so that correspondingly robust devices are used for their comminution, for example jaw crushers. After any pre-crushing, the agglomerates are then ground intensively, preferably wet, in a suitable mill. The grinding can be carried out in a single pass or preferably in several passes.
- the hexaaluminate is ground to the extent that it has a mean particle size D 50 of less than 3 microns.
- An average particle size D 50 is understood to be the value at which 50% of the particles kel smaller particle size and 50% have a larger particle size.
- the activity of the catalyst increases with increasing degree of comminution of the hexaaluminate.
- the average particle size D 50 is less than 2.5 microns, more preferably less than 2.0 microns and most preferably selected in the range of 0.5 to 1.9 microns. It has been found that the particle size distribution exerts no extraordinary influence on the activity of the catalyst. It is therefore not necessary to strive for the narrowest possible particle size distribution.
- D 70 is preferably chosen to be less than 6 ⁇ m, more preferably less than 4 ⁇ m, particularly preferably less than 3.8 ⁇ m, and particularly preferably in the range from 3.7 to 4.2 ⁇ m.
- composition of the hexaaluminate per se is that of hexaaluminates already proposed for use in the catalytic combustion of hydrocarbons.
- alkaline earth hexaaluminates are used, wherein both the alkaline earth metal and the aluminum may be partially replaced by other metals.
- Such other metals may be, for example, alkali metals or subgroup metals.
- the hexaaluminate is calcined before grinding at a temperature of more than 1050 0 C, more preferably more than 1100 0 C. Above 1000 0 C may advantageously form a mineral phase. By this measure, the hexaaluminate is largely insensitive to stresses below the calcination temperature.
- the hexaaluminate for example, in the above-described fuel cell assembly of a fuel cell assembly. exposure temperature in the range of 500 to 700 0 C, in particular about 650 0 C exposed. Since the hexaaluminate has already been calcined at a higher temperature, therefore, a long life of the catalytic burner is ensured.
- the calcination temperature can also be set higher if, for example, the catalytic burner is to be operated at a higher temperature than is required in combination with a fuel cell. For example, calcining temperatures of up to 1300 ° C. are also possible.
- the hexaaluminate is already calcined before grinding.
- the hexaaluminate is first subjected to a precalcination at low temperature and then a Hauptcalcin ist at a higher temperature.
- the calcination temperature of the precalcination is chosen to be relatively low, preferably in the range of 500 to 900 0 C, particularly preferably in the range of 600 to 800 0 C.
- the hexaaluminate is then preferably calcined again, with higher temperatures are used than at precalcination.
- the temperature at Hauptcalcinieren in the range 900-1400 0 C is preferred, particularly preferably in the range from 1050 to 1200 0 C selected. At these high temperatures, a mineral phase of the hexaaluminates can form.
- the hexaaluminates are characterized by a high hardness.
- the procedure during grinding is such that the hexaaluminate is slurried in water for grinding and then ground in a suitable mill, preferably a ball mill.
- the grinding process is preferably carried out in stages, the particle size of the hexaaluminate being gradually reduced. is being rectified.
- coarse grinding is preferably carried out between pre- and maincalcining. This coarse grinding is preferably carried out dry.
- the particle size D 50 of the coarse powder is preferably set in a range of 5 to 50 ⁇ m. Thereafter, this coarse powder is preferably slurried in water and ground wet in a fine grinding step to a very fine particle size.
- the preparation of the hexaaluminate is carried out in such a way that
- an aqueous solution of at least one alkaline earth nitrate is prepared
- the aqueous solution of the at least one alkaline earth nitrate is acidified to a pH of less than 2;
- an aqueous solution of (NH 4 ) 2 CO 3 which contains an excess of (NH 4 ) 2 CO 3 ;
- the clear aluminum-containing solution is added to the (NH 4 J 2 CO 3 solution, during which a pH of more than 7.5 is maintained, and
- the precipitated hexaaluminate is separated from the resulting mixture.
- the preparation by precipitation of the hexaaluminate from aqueous solution essentially follows the synthetic route described above, as described by Groppi et al. loc. cit. was found. This enables a cost-effective provision of the hexa-luminate, which can also be done on an industrial scale.
- an aqueous solution of an alkaline earth nitrate is first prepared.
- the corresponding alkaline earth nitrate is dissolved in deionized water. Possibly. can also be added to this solution, other metal salts, preferably also in the form of their nitrates.
- the alkaline earth metal nitrate solution is then acidified to a pH of less than 2, more preferably less than 1.
- nitric acid is used for this purpose.
- An aluminum salt is then added to the acidified aqueous alkaline earth metal nitrate solution, forming a clear solution.
- the aluminum salt used is aluminum nitrate, particularly preferably the nonahydrate.
- an aqueous solution of (NH 4 ) 2 CO 3 is provided, the concentration being selected to be high enough to provide an excess of (NH 4 J 2 CO 3 relative to the neutralization of the acidic aluminum-containing solution
- the (NH 4 ) 2 CO 3 solution is then introduced, preferably with vigorous stirring, into the clear aluminum-containing solution, the mixture being able to be heated, preferably to temperatures in the range from 50 to 80 ° C., preferably 55 to 70 ° C. during the addition of (NH 4) 2 CO 3 .roz is observed a vigorous evolution of gas.
- the pH of the mixture in the range of more than 7.5, preferably in The rate of addition of the acidic aluminum-containing solution may be adjusted accordingly.
- the resulting precipitate is aged.
- the aging is preferably carried out for a period of 30 minutes to 8 hours, more preferably for a period of 3 to 6 hours.
- the temperature of the slurry is preferably maintained in the range of 40 to 80 0 C, particularly preferably 50 to 70 0 C.
- the precipitate is then separated, preferably by filtration, washed with deionized water, preferably until nitrate can no longer be detected in the filtrate, and then dried at temperatures of preferably 90 to 140 0 C, particularly preferably 100 to 120 0 C.
- the solid obtained may optionally be pre-crushed to then, as described above, to be precalcined first at 500- 900 0 C, then dry pre-ground and after the main calcination at 1050-1200 0 C wet-ground wet.
- the hexaaluminate is a compound of the formula A 1 -z B z C x Al 2 - y 0i 9 - ⁇ , in which
- A at least one element from the group of Ca, Sr, Ba and
- Rb C at least one element from the group of Mn, Co, Fe and
- Cr z a value between 0 and 0.4
- x a value between 0.1 and 4
- - y a value between x and 2x
- oc a value determined by the valences of the other elements.
- ⁇ corresponds to a value which is determined by the valences of the other constituents and their content in the hexaaluminate.
- the value ⁇ results from:
- the individual components ie the metal salts, in particular nitrates of the metals A, B and C, are preferably in a ratio Al: (A * B): C of 100: (7 -10): (0.1 -4) used.
- Particularly preferred materials are BaMnAlnOig x and LaMnAliiOi 9-x , where x corresponds to the oxygen deficit.
- the hexaaluminate obtained by the process according to the invention has a low ignition point for the combustion of methane and shows a high activity even at relatively low temperatures, in particular in the range of 600 to 700 0 C, so that the combustion of the methane is complete and at high conversion rates.
- the invention therefore also relates to a catalyst as obtained by the process described above.
- the catalyst has a specific surface area of more than 6 m 2 / g, particularly preferably more than 15 m 2 / g.
- the catalyst according to the invention has a particle size with a D 50 of less than 3 ⁇ m at the end due to the intensive grinding carried out during the production.
- This particle size can also be determined on the finished catalyst.
- the finished catalyst can for example be scraped off a surface and the recovered powder can be screened to a particle size of 80 to 250 microns.
- the sieved powder is slurried in distilled water in an Erlenmeyer flask and the Erlenmeyer flask is kept in an ultrasonic bath for 30 minutes. Subsequently, the particle size distribution is measured under ultrasound and stirring for 1 minute.
- the catalyst according to the invention has a low ignition temperature for the combustion of methane and preferably an operating temperature in the range from about 600 to 700 ° C.
- the subject of the invention is therefore also a catalytic burner which satisfies the above-described contains a catalyst.
- the catalyst may be provided in particulate form, as a shaped body or preferably as a coating on a suitable carrier.
- the catalyst can be mixed with water and a suitable organic or inorganic binder and then extruded into Formk ⁇ rpern.
- the catalyst if appropriate mixed with a suitable binder, is slurried in water or another suitable solvent, for example an alcohol or alcohol / water mixture, and then applied to a suitable support by brushing, spraying or dipping.
- the carrier is preferably formed as a monolith.
- the catalyst can then be applied by simple dipping onto the surface of the monolith. After drying, the coating may optionally be fixed to the surface of the support by a calcination step.
- Such a coated monolith can be very easily installed in the exhaust stream, such as a fuel cell.
- the monolith preferably has a honeycomb structure.
- the catalytic burner according to the invention then has a plurality of parallel exhaust gas channels, which can also be connected through connection openings in the side surfaces of the channels in order to be able to compensate for pressure fluctuations within the gas flow.
- the monolith is preferably made of a ceramic material or of a suitable metal, for example a stainless steel, which can withstand the temperatures occurring in the gas stream during combustion, so that a long operating time of the catalytic burner is ensured.
- the catalytic burner according to the invention has a low ignition temperature for hydrocarbons, in particular methane. Furthermore, it is characterized by high conversion rates and an almost complete combustion of the supplied gases. It is therefore possible to reliably burn even small amounts of hydrocarbons, in particular methane, and hydrogen with the catalytic burner according to the invention.
- the catalytic burner according to the invention is therefore particularly suitable for use in a fuel cell arrangement for nearly complete combustion of the anode exhaust gas.
- the invention therefore also relates to a fuel cell arrangement with a number of fuel cells, which are arranged in a fuel cell stack, with an anode inlet for supplying fuel gas to the anodes of the fuel cell, an anode outlet for discharging the combusted fuel gas from the anodes, a cathode inlet to Supplying cathode gas to the cathodes of the fuel cells and a cathode outlet for discharging the spent cathode gas from the cathodes.
- a catalytic burner is provided at the anode outlet of the fuel cells, as described above, in which residues of hydrocarbons, in particular methane, and of hydrogen are burnt in after addition of air.
- a reformer for steam reforming of hydrocarbons, especially methane is provided, and a heat exchanger, with which heat generated in the catalytic burner is supplied to the reformer.
- the heat generated in the catalytic burner can be used for the treatment of the fuel gas.
- MCFC Molten Carbonate Fuel Cell
- the membrane between the anode and cathode compartment of the fuel cell is formed by a layer of a molten carbonate such as lithium potassium carbonate.
- the waste heat of the catalytic burner can be used to keep the carbonate in molten form.
- a cathode gas guide is provided, with which the exhaust gas emerging from the catalytic burner is supplied as cathode gas to the cathode inlet.
- the MCFC requires the provision of carbon dioxide to regenerate the carbonate on the cathode side. By recycling the exhaust gas generated in the catalytic burner as a cathode gas, the carbon dioxide contained can be used for the regeneration of the molten carbonate membrane.
- a protective housing which surrounds the fuel cell stack and the catalytic burner, wherein the fuel gas flow circulates within the protective housing.
- the fuel cell assembly can on the one hand be made very compact and on the other hand, the circulating gas streams can be optimally used for energy production.
- Fig. 1 a fuel cell assembly as described in DE 197 43 075 Al.
- Fig. 2 a particle size distribution of a hexaaluminate after four passes through a ball mill
- Fig. 3 a particle size distribution of a hexaaluminate after ten passes through a ball mill; 4 shows a representation of the methane conversion rate as a function of the temperature for a measurement gas which contains 1000 ppm of methane in air;
- Fig. 5 a representation of the methane conversion rate as a function of the temperature for a measurement gas which contains 1000 ppm of methane and 3000 ppm of hydrogen in air;
- FIG. 1 shows in a front view a section through a fuel cell arrangement, as shown in FIG. 2a of DE 197 430 75 A1, which, however, comprises the catalytic burner according to the invention.
- a protective housing 1 which is gas-tight and thermally insulating, there is a fuel cell assembly whose main component consists of a number of fuel cells arranged in a fuel cell stack 2.
- the fuel cells contain anodes (not shown), which are traversed vertically from bottom to top by a fuel gas B, and cathodes (not shown), which are flowed through in cross-flow to the anodes in the horizontal direction of a cathode gas.
- a fuel gas scrubber 3 is provided at the lower end of the fuel cell stack, via which fuel gas is fed to an anode inlet 4.
- the fuel gas scrubber separates the anode inlet 4 gas-tight from the interior of the protective housing 1.
- the fuel gas was in a reformer (not shown) produced from methane and water according to the water gas equilibrium and contains essentially hydrogen, carbon monoxide and carbon dioxide in addition to residues of unreacted methane and water.
- the fuel gas flows through the anode chamber of the fuel cell in the vertical direction and exits at the anode outlet 5 again from the anode chamber. After passing through a diffuser 6, in which a uniform gas flow is generated, the anode exhaust gas stream is sucked by an ejector 7.
- the ejector 7 is driven on the principle of a water jet pump by an air flow which is compressed by means of an external pump and then ejected through a nozzle.
- the ejector 7 is arranged in a separate space, which is bounded by the collecting hood 8 and the outer wall of the protective housing 1.
- the gas stream mixed with air is fed to a catalytic burner 9, in which combustible fractions of the anode exhaust gas still present in the gas stream are catalytically combusted.
- the combustion chamber of the catalytic burner 9 is coated with a hexaaluminate, which has been produced by the process according to the invention.
- the gas stream leaving the catalytic burner 9 is fed to the cathode inlet 10.
- a preheater and diffuser 11 is arranged, in which a uniform gas flow is generated.
- the gas flow with the aid of the preheater and diffuser 11 can be heated to the required operating temperature.
- thermal energy is sufficiently generated by the catalytic burner 9, so that the gas flow need not be additionally heated.
- the cathode gas stream enters the cathode compartments of the fuel cells at the cathode inlet 10 and passes through them in the horizontal direction to emerge from the cathode compartment again at the cathode outlet 12.
- the spent cathode exhaust gas passes through a heat exchanger 13, in which the cathode exhaust heat is removed. This heat is used to preheat the fuel gas. Subsequently, the cathode exhaust gas passes through a further heat exchanger 14, through which further heat is decoupled from the circulating cathode exhaust gas. This heat can be used for example for the production of the fuel gas in a reformer. Excess cathode exhaust gas is led out of the protective housing 1 via the exhaust gas guide A. The exhaust gas corresponds to the chemical equivalent of the fuel cell assembly supplied streams of fresh air L and fuel gas B.
- the operating point of the fuel cell assembly is set as the equilibrium state.
- the remaining cathode exhaust gas is mixed with the anode exhaust gas and fed via the feed hood 8 again to the ejector 7.
- the specific surface area is carried out on a fully automatic nitrogen porosimeter from Micromeritics, type ASAP 2010, in accordance with DIN 66131.
- the particle size is determined on the "Fritsch Particle Sizer Analysette 22" under ultrasound and stirring by laser diffraction, indicating the D 50 value, ie 50% of all particles ⁇ x ⁇ m.
- a solution of 12 kg of ammonium carbonate in 60 1 of demineralized water is prepared and heated to 55 0 C.
- a precipitation vessel with stirrer a little water is introduced and installed a pH probe. Then the two solutions are pumped simultaneously into the precipitation vessel at such speeds that the pH is maintained between 7.5 and 8. It is ensured that the pH does not fall below 7.5.
- the resulting suspension is aged for one hour and then the precipitate is separated by means of a filter press.
- the precipitate is washed with water at 70 ° C. and then separated by filtration.
- the precipitate is dried in a drying oven at 120 0 C for 48 h.
- the dried precipitate is coarsely ground (D50 ⁇ 20 microns) precalcined at 750 0 C and 3 h.
- the precalcined precipitate is then calcined again for 16 h at 1150 0 C.
- the powdered hexaaluminate is slurried in 4 liters of water and the slurry ground in a ball mill (Dyno-Mill, WA Bachofen, Switzerland), which has a grinding chamber with a volume of 250 ml, with Zirkonoxidku- gel with a diameter of 1 mm is filled.
- the suspension is pumped 4 times through the grinding chamber of 250 ml, whereby the speed of the mill is set to 4000 min -1
- the particle size distribution of the suspension after grinding is shown in FIG.
- the finely ground suspension is dried at 120 0 C.
- a suspension with a solids content of 50% is prepared in water.
- This suspension is either coated on catalyst support, such as honeycomb or placed in a mold in which the catalyst is to be used. After coating or shaping is dried again and calcined again at 450 0 C to achieve sufficient adhesion of the powder particles.
- a granulate is produced whose particles have a diameter of 250 to 500 ⁇ m.
- the granulated catalyst has a BET surface area of 19 m 2 / g.
- Example 1 Analogously to Example 1 is first BaMnAlnOi 9 - x produced.
- the calcined at 1150 0 C hexaaluminate is slurried in 5 1 of water.
- This suspension is pumped 10 times through a ball mill from the company Fryma (Rheinfelden) type MS-32 with 3.4 1 grinding chamber (2.4 1 balls lmm).
- This ball mill is an even more efficient annular gap ball mill.
- the suspension has a mean particle size D 50 of 0.93 microns. The particle size distribution is shown in FIG. 3a.
- the finely ground suspension is then dried at 120 0 C.
- a suspension is prepared in water, which has a solids content of 50%.
- catalyst support such as honeycomb bodies are coated or the suspension is brought into a form in which the catalyst is to be used.
- After the coating or shaping is dried again and calcined again at 450 0 C to produce a firm cohesion between the powder particles.
- a granulate is produced which has a diameter of 250-500 ⁇ m.
- a first container 650 g (2 mol) of lanthanum nitrate and 716 g of manganese nitrate (50% manganese) (2 mol) are initially charged and the container is made up to 25 l with demineralized water. The pH of the solution is washed with conc. Nitric acid adjusted to 1. Then 8.257 kg Aluminiumnitrat- 9-hydrate in the solution is added and the solution is heated to 60 0 C.
- a solution of 8 kg of ammonium carbonate in 45 1 of demineralized water is prepared and heated to 50 0 C.
- a precipitation vessel with stirrer a little water is introduced and installed a pH probe. Then the two solutions are pumped simultaneously into the precipitation vessel at such speeds that the pH remains between 7.5 and 8. The addition is carried out so that the pH does not fall below 7.5.
- the suspension is aged for one hour and then the precipitate is separated by filtration through a filter press.
- the solid obtained is washed once with 70 0 C with hot water and then again separated by filtration.
- the precipitate is dried in a drying oven at 120 0 C for 48 h.
- the dried precipitate is coarsely ground to an average particle size D 50 ⁇ 20 microns and the milled solid vorcalci- defined 3h at 750 0 C.
- the precalcined solid is again calcined 16h at 1100 0 C.
- the calcined at 1100 0 C hexaaluminate is slurried in 5 1 of water. This suspension is pumped 10 times through a ball mill from the company Fryma (Rheinfelden) type MS-32 with 3.4 1 grinding chamber (2.4 1 balls lmm). The mean particle size D 50 of the solid contained in the suspension was found to be 0.88 ⁇ m. The particle size distribution is shown in FIG. 3b.
- the finely ground suspension is dried at 120 0 C and made from the dry powder again a suspension in water with 50% solids.
- a catalyst support such as a honeycomb body can be coated or the hexaaluminate is brought into a form in which the catalyst is to be used.
- the catalyst is then dried again and calcined again at 450 ° C. in order to achieve sufficient adhesion between the grains of the catalyst.
- a granulate with a diameter of 250 to 500 ⁇ m is produced from the powdered hexaaluminate.
- Example 2 Analogously to Example 1, a hexaaluminate is prepared. After calcining at 1150 0 C only dry is also ground to the grain size 250-500 microns.
- a granulate with a diameter of 250 to 500 ⁇ m is produced from the powdered hexaaluminate.
- the catalyst granules prepared in Examples 1 to 4 are tested in a microreactor for the oxidation of methane and hydrogen.
- the granules are introduced into a reactor with 8 mm inner diameter.
- a gas mixture of 1000 ppm methane in synthetic air (20% O 2 /80% N 2 ) or a gas mixture with 1000 ppm methane and 3000 ppm hydrogen in synthetic air is used at a space velocity of 40,000 hours "1 through the reactor, with the aid of this gas mixture conversion curves being produced as a function of the temperature are shown in FIGS. 4 and 5.
- the test gas used was a gas containing 1000 ppm of methane in air.
- the GHSV was 40000 h '1 . It can be seen that the activity of the catalyst increases with decreasing particle size.
- FIG. 5 shows the conversion of methane as a function of the temperature for catalysts ground to a different degree.
- the conversion rate for methane is only slightly affected by the presence of hydrogen.
- the catalyst LaMnAli 1 Oi 9 - X shows at 600 0 C a conversion rate of more than 90%. At 450 0 C, a conversion rate of 20% is already achieved.
- the ignition temperature for hydrogen is 200 0 C.
- the catalyst is therefore suitable at temperatures of more than 200 0 C as a catalytic burner for the anode exhaust gas of a fuel cell. It is only necessary to ignite the catalyst to heat it to a temperature of about 200 0 C. Subsequently, the required temperature is adjusted and maintained by controlling the mass and heat flows in the fuel cell.
- a small platinum precatalyst may be provided, in which the hydrogen can be ignited at lower temperatures.
- Example 6 Determination of the Particle Size Distribution of a Catalyst from the Washcoat after Coating
- 500 g of the powder are stirred in portions using 500 ml of water using an Ultra-Turrax-stirrer. As soon as the viscosity of the suspension increases, a total of 6 g of concentrated acetic acid are added dropwise in each case.
- the suspension is then ground again briefly in a ball mill (Dyno-mill ⁇ s , WAB, Switzerland) filled with 1 mm diameter zirconia balls. Subsequently, the suspension is spread to a thin film and dried. The dried coating is scraped off and the recovered powder sieved to a particle size of 80 to 250 microns.
- 100 mg of the sieved powder are slurried in 100 ml of distilled water in an Erlenmeyer flask and the Erlenmeyer flask is kept in an ultrasonic bath for 30 minutes.
- the particle size distribution is then measured in a Fritsch Particle Sizer Analysette 22 under ultrasound and with stirring for 1 minute.
- the measured curves are reproduced in FIGS. 6 a to d. Only in the case of the previously finely ground samples is a reduced mean particle diameter D 50 of less than 1.5 ⁇ m found in the removed washcoat.
- a D 50 value of 3.06 ⁇ m is found for the unmilled catalyst and a D 50 value of 1.16 ⁇ m for the milled catalyst.
- a D 50 value of 5.21 ⁇ m is found for the unmilled catalyst, and a D 50 value of 1.44 ⁇ m for the milled catalyst.
- the particle size of the catalyst leaves Therefore, they also determine from the catalyst coating applied on a support.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005062926A DE102005062926A1 (de) | 2005-12-29 | 2005-12-29 | Brennstoffzellenanordnung mit edelmetallfreiem Abgasbrenner |
PCT/EP2006/012589 WO2007079976A1 (de) | 2005-12-29 | 2006-12-28 | Auf einem hexaaluminat basierender katalysator für die verbrennung von kohlenwasserstoffen sowie brennstoffzellenanordnung mit abgasbrenner |
Publications (1)
Publication Number | Publication Date |
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EP1968742A1 true EP1968742A1 (de) | 2008-09-17 |
Family
ID=38045515
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP06829897A Withdrawn EP1968742A1 (de) | 2005-12-29 | 2006-12-28 | Auf einem hexaaluminat basierender katalysator für die verbrennung von kohlenwasserstoffen sowie brennstoffzellenanordnung mit abgasbrenner |
Country Status (5)
Country | Link |
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US (1) | US20090226780A1 (de) |
EP (1) | EP1968742A1 (de) |
KR (1) | KR20080074891A (de) |
DE (1) | DE102005062926A1 (de) |
WO (1) | WO2007079976A1 (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102007037796A1 (de) | 2007-08-10 | 2009-02-12 | Süd-Chemie AG | Verfahren zur Entfernung von CO, H2 und/oder CH4 aus dem Anodenabgas einer Brennstoffzelle mit Mischoxidkatalysatoren umfassend Cu, Mn und gegebenenfalls mindestens ein Seltenerdmetall |
JP5431158B2 (ja) * | 2008-02-21 | 2014-03-05 | 株式会社エフ・シー・シー | 触媒担体又は触媒及びその製造方法 |
DE102008016578A1 (de) * | 2008-04-01 | 2009-10-08 | Daimler Ag | Brennstoffzelleneinrichtung und Verfahren zum Betreiben einer Brennstoffzelleneinrichtung |
DE102008016579A1 (de) * | 2008-04-01 | 2009-10-08 | Daimler Ag | Brennstoffzelleneinrichtung und Verfahren zum Betreiben einer Brennstoffzelleneinrichtung |
KR101127649B1 (ko) * | 2009-07-03 | 2012-03-23 | 두산중공업 주식회사 | 용융탄산염 연료전지에 사용되는 수소 연소용 촉매 및 이의 제조방법 |
AT508488A1 (de) | 2009-07-13 | 2011-01-15 | Vaillant Group Austria Gmbh | Nachbrenner für erdgasbasierte brennstoffzellenheizgeräte |
US9192917B2 (en) * | 2010-07-08 | 2015-11-24 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas purifying catalyst and production method for same |
DE102014219836A1 (de) * | 2014-09-30 | 2016-05-25 | Volkswagen Aktiengesellschaft | Brennstoffzellenanordnung mit Strahlpumpe in Abgaspfad und Kraftfahrzeug mit Brennstoffzellenanordnung |
KR101688894B1 (ko) * | 2016-08-08 | 2016-12-23 | 주식회사 지엔티엔에스 | 고온 연소촉매를 이용한 버너 |
AT520881B1 (de) * | 2018-01-17 | 2020-04-15 | Avl List Gmbh | Verfahren zum Betreiben eines Brennstoffzellensystems |
Family Cites Families (7)
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US4771028A (en) * | 1985-08-30 | 1988-09-13 | Catalysts And Chemicals Inc. | Heat resistant composition and method of producing the same |
DE3770920D1 (de) * | 1986-12-03 | 1991-07-25 | Catalyst And Chemicals Inc Far | Feuerfester katalysator und verfahren zu seiner herstellung. |
FR2743008B1 (fr) * | 1995-12-28 | 1998-01-30 | Inst Francais Du Petrole | Procede de combustion catalytique a plusieurs zones catalytiques successives |
US6413489B1 (en) * | 1997-04-15 | 2002-07-02 | Massachusetts Institute Of Technology | Synthesis of nanometer-sized particles by reverse micelle mediated techniques |
DE19743075A1 (de) * | 1997-09-30 | 1998-12-24 | Mtu Friedrichshafen Gmbh | Brennstoffzellenanordnung mit interner Kathodengaszirkulation |
US7604673B2 (en) * | 2003-06-27 | 2009-10-20 | Ultracell Corporation | Annular fuel processor and methods |
US20070111884A1 (en) * | 2005-11-14 | 2007-05-17 | Laiyuan Chen | Catalyst support, supported catalyst, and methods of making and using the same |
-
2005
- 2005-12-29 DE DE102005062926A patent/DE102005062926A1/de not_active Withdrawn
-
2006
- 2006-12-28 EP EP06829897A patent/EP1968742A1/de not_active Withdrawn
- 2006-12-28 US US12/159,268 patent/US20090226780A1/en not_active Abandoned
- 2006-12-28 WO PCT/EP2006/012589 patent/WO2007079976A1/de active Application Filing
- 2006-12-28 KR KR1020087011944A patent/KR20080074891A/ko not_active Application Discontinuation
Non-Patent Citations (1)
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See references of WO2007079976A1 * |
Also Published As
Publication number | Publication date |
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DE102005062926A1 (de) | 2007-07-05 |
WO2007079976A1 (de) | 2007-07-19 |
US20090226780A1 (en) | 2009-09-10 |
KR20080074891A (ko) | 2008-08-13 |
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