WO2004000458A1 - 改質ガス中の一酸化炭素の選択酸化触媒 - Google Patents
改質ガス中の一酸化炭素の選択酸化触媒 Download PDFInfo
- Publication number
- WO2004000458A1 WO2004000458A1 PCT/JP2002/006278 JP0206278W WO2004000458A1 WO 2004000458 A1 WO2004000458 A1 WO 2004000458A1 JP 0206278 W JP0206278 W JP 0206278W WO 2004000458 A1 WO2004000458 A1 WO 2004000458A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alumina
- carbon monoxide
- selective oxidation
- catalyst
- reformed gas
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 50
- 230000003647 oxidation Effects 0.000 title claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- -1 isocyanatoethyl Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
Classifications
-
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0248—Coatings comprising impregnated particles
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
- C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
-
- 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
-
- 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
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/462—Ruthenium
-
- B01J35/393—
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/044—Selective oxidation of carbon monoxide
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a catalyst for selectively oxidizing carbon monoxide in a reformed gas, and more particularly, to a catalyst in a reformed gas used for a fuel cell operating at a low temperature, particularly a polymer electrolyte fuel cell.
- the present invention relates to a catalyst for selectively oxidizing carbon oxide.
- reformed gas obtained by steam reforming hydrocarbons of natural gas such as methane and propane, alcohol such as methanol, and naphtha, etc.
- Such reformed gas contains carbon monoxide in addition to hydrogen, carbon dioxide, etc., and contains about 1 V o 1% carbon monoxide even after being subjected to the shift reaction. Is known to be.
- Such by-produced carbon monoxide is also used as a fuel in a high-temperature operation type fuel cell such as a molten carbonate type.
- a phosphoric acid type or solid polymer type low temperature operation type fuel cell an electrode catalyst is used.
- a polymer electrolyte fuel cell that operates at a lower temperature than a phosphoric acid fuel cell, it exhibits a catalytic poisoning effect on a platinum-based catalyst that is Poisoning was significant, and the problem of reduced power generation efficiency arose.
- the coexisting carbon monoxide in order to obtain the required power generation efficiency while using reformed gas, the coexisting carbon monoxide must be reduced from about 1 V o 1 ° / 0 to 110 Although it is necessary to supply after the reduction, the conventional platinum-alumina catalyst does not sufficiently reduce the oxidation of carbon monoxide, and the remaining carbon monoxide causes deterioration of power generation efficiency.
- the present inventors have studied the selective oxidation catalyst for carbon monoxide using alumina as a carrier.
- the alumina carrier contains an oxide or the like of a specific element in a certain amount or more, the activity of the selective oxidation catalyst becomes remarkable. Was found to be reduced. '' Disclosure of the invention
- the present invention has been made in view of such problems of the conventional technology, and has as its object to selectively oxidize and reduce carbon monoxide in a reformed gas to achieve good fuel utilization.
- An object of the present invention is to provide a carbon monoxide selective oxidation catalyst capable of realizing efficiency and power generation efficiency.
- the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, by supporting ruthenium platinum on an alumina carrier having an appropriately controlled specific impurity content, oxygen gas was converted to carbon monoxide.
- the present inventors have found that excellent selective oxidation of carbon monoxide is performed under excessively existing conditions, thereby completing the present invention.
- the catalyst for selective oxidation of carbon monoxide of the present invention comprises: Is a catalyst that selectively oxidizes with oxygen gas,
- Ruthenium and / or platinum are carried on an alumina carrier containing ⁇ - alumina, and the sodium contained in the alumina carrier is less than 0.07% by Na 2 conversion. It is characterized by.
- still another carbon monoxide selective oxidation catalyst of the present invention is a catalyst for selectively oxidizing carbon monoxide in a reformed gas with oxygen gas
- the aluminum and alumina carriers containing alumina and Z or platinum are supported on the alumina-containing support, and the alumina carriers are supported on a magnesium-containing support.
- the magnesium contained in the alumina carrier supporting ruthenium and z or platinum is less than 0.04% in terms of MgO.
- still another preferred embodiment of the selective oxidation catalyst for carbon monoxide of the present invention is such that sodium is contained in the alumina carrier supporting ruthenium and Z or platinum, and the sodium content is N. a characterized by less than 0.07% in terms of 2 2
- the catalyst metals ruthenium (Ru) and platinum (Pt) are present near the outermost surface of the carrier.
- the temperature at which CO oxidation occurs can be shifted to a lower temperature, and the selectivity with respect to other reactions can be improved. It is thought that the concentration of CO in the reformed gas afterwards can be reduced and the consumption of hydrogen can be prevented.
- Co selective oxidation catalyst of the present invention by using extremely high purity alumina as a carrier, high Co oxidation activity can be expressed, so that Ru and / or Pt can be added to aluminum. If a metal other than the catalytically active noble metal species, such as sodium or its metal oxide, is contained, it is considered that the adsorption form of the reaction gas changes and the activity is greatly inhibited.
- a so-called honeycomb-shaped support can be used, but magnesium or the like derived from the honeycomb-shaped support is also a causative substance for reducing the catalytic activity. Therefore, it is desirable to control the amount of these mixed in ⁇ -alumina to a certain value or less.
- the carbon monoxide selective oxidation catalyst of the present invention is a catalyst that selectively oxidizes C 2 O in a reformed gas with oxygen gas.
- the reformed gas generally refers to a gas obtained by steam reforming a hydrocarbon such as methane or propane, an alcohol such as methanol, or naphtha, and the like. a main component of hydrogen gas, carbon dioxide (C 0 2), methane (CH 4), containing water (H 2 0) and CO.
- an effective object to which the present invention is applied is a reformed gas after the shift reaction, and a CO concentration of about 1 Vo 1%.
- the oxygen gas is not particularly limited as long as it is present in excess of the reaction equivalent with co, but typically, oxygen gas of 1.1 to 5 times the reaction equivalent with CO is used. Preferably, it is present.
- the selective oxidation catalyst of the present invention preferably contains Ru and Pt at a ratio of 0.01 to 10%. That is, loading of a mixture of R u and P t is preferably set to 0.0 1-1 0% of the total catalyst obtained, preferably be 0.0 2 to 0.5 0/0 Good.
- the supported amount of the above mixture is less than 0.02%, the oxidation activity of CO may not be sufficient, and if it exceeds 0.5%, Ru and Pt may not be used effectively.
- the selective oxidation catalyst of the present invention it is preferable that at least one of the supported Ru and Pt has a particle diameter of 200 A or less, preferably 5 to 200 A.
- the oxidation activity of co may be insufficient, which is not preferable.
- an alumina carrier is used.
- the alumina carrier is contained, and a mixture of Ru, Pt, and Ru-Pt is formed from the surface of the alumina particles constituting the carrier.
- the shape is not limited as long as it is an alumina support that can be present within ⁇ , preferably within ⁇ .
- ⁇ -alumina can be suitably used as a carrier. This is because ⁇ -alumina does not have fine pores, This is because localization is easily realized, and the effect of water vapor can be reduced as described above.
- alumina may be used alone, it can be used in combination with other crystalline alumina.
- ⁇ -alumina transforms to ⁇ -alumina when kept at a temperature of 100 ° C or more, but when kept at that temperature, the catalytic metals Ru and Pt cause sintering, and It is not suitable for use alone in the catalyst of the present invention, since no activity can be obtained.
- alumina such as ⁇ , ⁇ , etc. is heat-treated and phase-converted to alumina, and then used as a carrier. It is possible to use high-purity alumina of various crystal systems together with alumina.
- the alumina support preferably contains an extremely high concentration of ⁇ -alumina, and contains a certain amount or more of impurities such as sodium (Na) and magnesium (Mg). And may inhibit the catalytic activity.
- the content of Na in the alumina carrier needs to be controlled to less than 07% in terms of Na 2 a.
- the selective oxidation catalyst of the present invention can be in the form of granules or pellets.
- a honeycomb-shaped support can be used.
- a honeycomb-shaped honeycomb made of cordierite or metal can be used. It is also possible to coat and use the above-mentioned integral structure type support.
- magnesium derived from cordierite (Mg) The content of the above alumina carrier in the above-mentioned alumina carrier is 0. It must be controlled to less than 0 4%.
- the selective oxidation catalyst of the present invention has the above-described configuration, and has excellent CO selection. Although it is oxidizing, it typically oxidizes and removes about 1 V ⁇ 1% of CO that coexists in the reformed gas to about 100 ppm.
- FIG. 1 is a graph showing the dependency of the catalytic performance of the CO selective oxidation catalyst on the Na mixing ratio
- FIG. 2 is a graph showing the catalytic performance of the CO selective oxidation catalyst containing Mg.
- Methane concentration 2% Reaction temperature; 100 to 250 ° C
- the catalyst was pulverized, and the supported metal was directly observed with a transmission electron microscope to confirm the particle size.
- the catalyst was divided into almost half and the cross section was observed by EPMA to confirm the supported width.
- the surface of the catalyst was observed by XPS, and the noble metal concentration on the alumina surface was confirmed.
- Ru was supported on high-purity alumina having an average particle diameter of about 2 mm (alumina concentration: 9.9.995%) to obtain a selective oxidation catalyst A of this example.
- Ru was present at a depth of 50 m from the outer surface of the alumina particles.
- the Ru particle size was about 100 A on average.
- Example 2 Except that the feedthrough at a rate of 0.0 1 4% the high-purity ⁇ -alumina with N a in N a 2 0 translation, the same procedure as in Example 1 to obtain a selective oxidation catalyst of this example. The CO concentration was measured in the same manner as in Example 1, and the obtained results are shown in FIG.
- Example 1 Except that mixed with N a to the high-purity ⁇ -alumina in a proportion of 0.0 7% N a 2 0 in terms of the selective oxidation catalyst of this example the same procedure as in Example 1 Obtained.
- the CO concentration was measured in the same manner as in Example 1, and the obtained results are shown in FIG. FIG. 1 shows that the selective oxidation catalysts of Examples 1 and 2 exhibit excellent CO selective oxidation activity.
- CO could be reduced to the target concentration in a wide temperature range from a low temperature to a high temperature.
- the selective oxidation catalyst of Comparative Example 1 the CO concentration was 1 OOOO ppm unchanged from the supply, and the CO concentration was 300 ppm in the range of 150 ° C to 200 ° C. Was low.
- Mg is mixed with 0.02% in terms of MgO into high-purity alumina (alumina concentration: 9.9.995%) with an average particle size of about 2 mm, and about 0.2% of Ru is further supported.
- a selective oxidation catalyst of this example was obtained.
- the application of the selective oxidation catalyst of the present invention is not limited to the reformed gas supplied to the polymer electrolyte fuel cell, but can also be used to reduce the co in the reformed gas. Therefore, it can be applied to various processes such as synthesis of ammonia which requires high purity hydrogen gas. Industrial applicability
Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002315872A AU2002315872A1 (en) | 2002-06-24 | 2002-06-24 | Catalysts for selective oxidation of carbon monoxide in reformed gas |
JP2004515455A JPWO2004000458A1 (ja) | 2002-06-24 | 2002-06-24 | 改質ガス中の一酸化炭素の選択酸化触媒 |
PCT/JP2002/006278 WO2004000458A1 (ja) | 2002-06-24 | 2002-06-24 | 改質ガス中の一酸化炭素の選択酸化触媒 |
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PCT/JP2002/006278 WO2004000458A1 (ja) | 2002-06-24 | 2002-06-24 | 改質ガス中の一酸化炭素の選択酸化触媒 |
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WO2004000458A1 true WO2004000458A1 (ja) | 2003-12-31 |
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JP (1) | JPWO2004000458A1 (ja) |
AU (1) | AU2002315872A1 (ja) |
WO (1) | WO2004000458A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013103149A (ja) * | 2011-11-11 | 2013-05-30 | Tanaka Kikinzoku Kogyo Kk | 水蒸気改質触媒 |
US9993812B2 (en) | 2012-04-17 | 2018-06-12 | Momentive Pereformance Materials Inc. | High activity catalyst for hydrosilylation reactions and methods of making the same |
US20190070592A1 (en) * | 2007-03-01 | 2019-03-07 | Velocys Technologies Limited | Promoted carbide-based fischer-tropsch catalyst, method for its preparation and uses thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0459048A (ja) * | 1990-06-19 | 1992-02-25 | Sekiyu Sangyo Kasseika Center | 水蒸気改質用の触媒 |
WO2000017097A1 (en) * | 1998-09-21 | 2000-03-30 | Shell Internationale Research Maatschappij B.V. | Catalysts for the selective oxidation of carbon monoxide in hydrogen-containing gases |
JP2001017861A (ja) * | 1999-07-05 | 2001-01-23 | Tanaka Kikinzoku Kogyo Kk | 改質ガス中の一酸化炭素の選択酸化触媒 |
JP2001212458A (ja) * | 2000-02-04 | 2001-08-07 | Tanaka Kikinzoku Kogyo Kk | 改質ガス中の一酸化炭素の選択酸化触媒 |
-
2002
- 2002-06-24 JP JP2004515455A patent/JPWO2004000458A1/ja active Pending
- 2002-06-24 AU AU2002315872A patent/AU2002315872A1/en not_active Abandoned
- 2002-06-24 WO PCT/JP2002/006278 patent/WO2004000458A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0459048A (ja) * | 1990-06-19 | 1992-02-25 | Sekiyu Sangyo Kasseika Center | 水蒸気改質用の触媒 |
WO2000017097A1 (en) * | 1998-09-21 | 2000-03-30 | Shell Internationale Research Maatschappij B.V. | Catalysts for the selective oxidation of carbon monoxide in hydrogen-containing gases |
JP2001017861A (ja) * | 1999-07-05 | 2001-01-23 | Tanaka Kikinzoku Kogyo Kk | 改質ガス中の一酸化炭素の選択酸化触媒 |
JP2001212458A (ja) * | 2000-02-04 | 2001-08-07 | Tanaka Kikinzoku Kogyo Kk | 改質ガス中の一酸化炭素の選択酸化触媒 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190070592A1 (en) * | 2007-03-01 | 2019-03-07 | Velocys Technologies Limited | Promoted carbide-based fischer-tropsch catalyst, method for its preparation and uses thereof |
JP2013103149A (ja) * | 2011-11-11 | 2013-05-30 | Tanaka Kikinzoku Kogyo Kk | 水蒸気改質触媒 |
US9993812B2 (en) | 2012-04-17 | 2018-06-12 | Momentive Pereformance Materials Inc. | High activity catalyst for hydrosilylation reactions and methods of making the same |
Also Published As
Publication number | Publication date |
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AU2002315872A1 (en) | 2004-01-06 |
JPWO2004000458A1 (ja) | 2005-10-20 |
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