US20040058810A1 - Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture - Google Patents
Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture Download PDFInfo
- Publication number
- US20040058810A1 US20040058810A1 US10/669,271 US66927103A US2004058810A1 US 20040058810 A1 US20040058810 A1 US 20040058810A1 US 66927103 A US66927103 A US 66927103A US 2004058810 A1 US2004058810 A1 US 2004058810A1
- Authority
- US
- United States
- Prior art keywords
- carbon monoxide
- catalyst
- gas mixture
- shift catalyst
- conversion
- 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.)
- Abandoned
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 70
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000006262 metallic foam Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- -1 open-cell Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YYAVXASAKUOZJJ-UHFFFAOYSA-N 4-(4-butylcyclohexyl)benzonitrile Chemical compound C1CC(CCCC)CCC1C1=CC=C(C#N)C=C1 YYAVXASAKUOZJJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000002211 methanization Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- 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
-
- B01J35/56—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a method for catalytic conversion of carbon monoxide with water to carbon dioxide and hydrogen in a gas mixture that contains hydrogen and other oxidizable components.
- reaction in accordance with reaction equation (1) is called carbon monoxide conversion or CO conversion herein.
- water gas shift reaction is commonly used for this in the USA.
- Both the known high-temperature and the low-temperature catalysts are bulk catalysts, in which the catalyst material is pressed to form pellets or other molded bodies. Accordingly, they consist entirely of catalytically active mass and are also called complete catalysts. As a rule, they have a very high bulk weight.
- reaction equation (1) The known industrial methods for conversion of carbon monoxide on catalysts according to reaction equation (1) operate at space velocities of the gas mixture between 300 and 3000 h ⁇ 1 . These low velocities are not sufficient for use in motor vehicles.
- R CO for the carbon monoxide, which is understood within the scope of this invention to mean the amount of carbon monoxide N CO converted per weight of the catalyst m cat and reaction time ⁇ t.
- the known Cu/ZnO and Fe/Cr catalysts have to be activated by reduction before they are used.
- the activated catalysts are sensitive to oxygen. Upon contact with atmospheric oxygen they are reoxidized and deactivated in an exothermic reaction.
- D. C. Grenoble et al. describe in “The Chemistry and Catalysis of the Water Gas Shift Reaction. 1. The Kinetics over Supported Metal Catalysts,” J. Catal. 67 (1980) 90-102, powdered catalysts that contain Cu, Re, Co, Ru, Ni, Pt, Os, Au, Fe, Pd, Rh or Ir as active components and that are deposited on aluminum oxide (Al 2 O 3 ) as a support material. The kinetic tests gave a reaction order of about 0.2 for carbon monoxide and about 0.5 for the water that was used.
- an object of the present invention is to provide a method for conversion of carbon monoxide in a hydrogen-containing gas mixture that, under the conditions of mobile use in motor vehicles with their rapidly changing power requirements, a high specific conversion rate for carbon monoxide with good selectivity, has high temperature stability and is insensitive to oxygen in the educt gas mixture.
- This above and other objects of the invention can be achieved by a method for catalytic conversion of carbon monoxide to carbon dioxide and hydrogen (carbon monoxide conversion) in a hydrogen-containing gas mixture.
- the gas mixture is passed over a shift catalyst, which is at the operating temperature for carbon monoxide conversion.
- the method features a shift catalyst based on noble metals that is applied to an inert carrier in the form of a coating.
- the method of the present invention is specifically directed to mobile use in motor vehicles powered by fuel cells in order to effectively removed carbon monoxide from the hydrogen-rich gas mixture that is obtained by steam reforming, partial oxidation or autothermic reforming (hereinafter also called reformate gas) under all conditions of operation of the motor vehicle.
- the gas mixture can contain up to 40 vol % carbon monoxide, depending on its production.
- the mobile use of the method imposes high requirements on its efficiency and dynamics.
- the catalysts are loaded with very different space velocities. They vary between a low space velocity at idling and 100,000 h ⁇ 1 at full load.
- the method of the invention enables a high efficiency, i.e., a high space-time yield through the application of the catalyst in the form of a coating onto an inert carrier.
- a catalyst is also called a coating catalyst herein.
- the monolithic honeycomb elements of ceramic or metal with cell densities (number of flow channels per area of cross section) of more than 10 cm ⁇ 2 that are known from auto exhaust treatment are suitable as carrier.
- metal sheet, heat exchanger plates, open-cell ceramic or metal foam elements and irregularly shaped elements formed in each case according to requirements can also be used as carriers.
- the thickness of the coating can vary between 10 and 100 ⁇ m according to application.
- a carrier within the scope of this invention is characterized as inert if the material of the carrier does not participate or participates only negligibly in the catalytic conversion. As a rule, these are bodies with low specific surface and low porosity.
- a catalyst that contains the elements of the platinum group of metals, thus platinum, palladium, rhodium, iridium, ruthenium and osmium, or gold as the catalytic active components on an oxide support made from the group consisting of aluminum oxide, silicon dioxide, titanium oxide, rare earth oxides or mixed oxides of these or zeolites is suitable for the proposed method.
- the support material should have at least a specific surface (BET surface, measured in accordance with DIN 66132) of more than 10 m 2 /g.
- This noble metal catalyst exhibits a shift activity, i.e., it is capable, if the appropriate reaction conditions exist (temperature, gas composition), of converting carbon monoxide with water in accordance with reaction equation (1) to carbon dioxide and hydrogen. For this reason it is also called a noble metal shift catalyst herein. Its shift activity and selectivity can be improved by the addition of other catalytically active components, or promoters. Among these are elements of the rare earth metals, in particular cerium and lanthanum, as well as the non-noble metals of the subgroups of the periodic system of elements, especially iron or copper.
- the shift activity and selectivity can, moreover, also be increased by doping the support material with redox-active oxides of the metals cerium, zirconium, titanium, vanadium, manganese and iron in an amount of 1 to 50 wt % with respect to the total weight of the support material.
- a preferred shift catalyst for the method in accordance with the invention contains platinum and/or palladium together with iron or copper as well as cerium oxide on a finely divided aluminum oxide.
- the described catalyst material is not processed to complete catalysts, but rather is applied in the form of a coating to inert supports.
- the disadvantages of complete catalysts that consist of the catalytically active centers in the interior of the complete catalyst being poorly accessible to the reactants are avoided in this method. Poor accessibility reduces the specific conversion rate for carbon monoxide and thus the achievable space-time yield. This has the corresponding negative effects on the volume of the required reactor.
- the vibrations caused by operation of the motor vehicle additionally lead to undesired abrasion of complete catalysts, which blocks the flow paths in the catalyst bed and thus continuously increases the pressure difference in the reactor.
- the process operates at gas mixture space velocities from idling space velocity up to a value of 100,000 h ⁇ 1 and at a pressure between atmospheric pressure and 10 bar, where the space velocity is given in reference to the volume of carrier coated with the catalyst.
- the method can be used both for low-temperature CO conversion as well a for high-temperature CO conversion.
- a noble metal shift catalyst with an operating temperature between 180 and 300° C. is used for the low-temperature CO conversion.
- the low operating temperature is achieved through a relatively high charge of catalytically active noble metals on the catalyst.
- the reformate gas usually contains 2 to 15 vol % carbon monoxide and has an input temperature between 100 and 250° C. which results from the reforming process.
- a noble metal shift catalyst with an operating temperature between 280 and 550° C. is used for the high temperature CO conversion.
- the reformate gas usually contains 2 to 40 vol % carbon monoxide and has an input temperature between 300 and 600° C., which results from the reforming process.
- the method also allows a high temperature conversion stage and a low temperature conversion stage to be connected in succession.
- the gas mixture in this case leaves the high temperature stage at a temperature that corresponds to the operating temperature of the catalyst of the high temperature stage and for this reason has to be cooled to the operating temperature of the catalyst of the low-temperature stage before contact with it.
- the support material for the catalytically active components can be suspended in an aqueous solution of soluble compounds of a noble metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, osmium, gold and mixtures thereof and other soluble compounds of non-noble metals of the subgroups.
- a noble metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, osmium, gold and mixtures thereof and other soluble compounds of non-noble metals of the subgroups.
- the acid suspension is neutralized at elevated temperature with a base, for example, a sodium carbonate, and then reduced at the same temperature with an aqueous reducing agent (formaldehyde, hydrazine), filtered, washed, dried, calcined in an oxidizing atmosphere at temperatures between 300 and 550° C., and then reduced at temperatures between 300 and 600° C.
- a base for example, a sodium carbonate
- an aqueous reducing agent formaldehyde, hydrazine
- the catalyst material is again suspended in water to produce a coating suspension.
- the carrier element is coated with this suspension.
- the methods for coating carrier elements that are known from auto exhaust catalysis can be used.
- the coating is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
- the carrier element is first coated only with the support material, where the support material can contain rare earth oxides and oxides of non-noble metals of the subgroups.
- the coating on the carrier element is then impregnated with a solution of at least one soluble noble metal compound, soluble compounds of the rare earths and the non-noble metals of the subgroups.
- the coated carrier element is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
- Another variation for making a coating catalyst in accordance with the invention resides in first producing a suspension of the support material, the soluble compounds of the noble metals and optionally the soluble compounds of the non-noble metals of the subgroups and the rare earths. The dissolved components of the suspension are then precipitated onto the suspended support material through the addition of a basic precipitation agent such as sodium hydroxide. The suspension prepared in this way is used directly for coating the carrier element. To finish the production of the coating catalyst, the coated carrier element is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
- a noble metal shift catalyst (catalyst A) was produced as follows:
- a ceramic element honeycomb carrier with 93 cells per square centimeter and a volume of 0.041 L was coated with 7.25 g ⁇ -aluminum oxide by immersing it in an aqueous suspension of ⁇ -aluminum oxide (specific surface 140 m 2 /g) and calcining for 2 h at 600° C. After calcination the coated honeycomb element was impregnated with a solution of Ce(NO 3 ) 2 .6H 2 O and then calcined for 2 h at 500° C. The calcined molded element was then impregnated with a solution of Pt(NO 3 ) 2 , Pd(NO 3 ) 2 and Fe(NO 3 ) 3 .
- the catalytically active coating of the catalyst prepared in this way had a total weight of 5.16 g, which corresponds to 126 g per liter of volume of the honeycomb element. It contained 1.2 wt % Pt, 1.2 wt % Pd, 2.4 wt % Fe, 35.7 wt % CeO 2 and 59.5 wt % Al 2 O 3 .
- German priority application 100 13 895.0 is relied on and incorporated herein by reference.
Abstract
A method for catalytic conversion of carbon monoxide with water to carbon dioxide and water in a hydrogen-containing gas mixture (carbon monoxide conversion) by passing the gas mixture over a shift catalyst that is at an operating temperature for the carbon monoxide conversion. The method is carried out with a shift catalyst based on noble metals that is applied to an inert support element in the form of a coating.
Description
- The present invention relates to a method for catalytic conversion of carbon monoxide with water to carbon dioxide and hydrogen in a gas mixture that contains hydrogen and other oxidizable components.
- The conversion of carbon monoxide with water to carbon dioxide and hydrogen in the presence of catalysts is a known method for producing hydrogen-rich gas mixtures, which is based on the following exothermic reaction:
- CO+H2O⇄H2+CO2 ΔH>0 (1)
-
- The reaction in accordance with reaction equation (1) is called carbon monoxide conversion or CO conversion herein. The term “water gas shift reaction” is commonly used for this in the USA.
- The production of hydrogen-rich gas mixtures from hydrocarbons, or alcohols, by steam reforming, partial oxidation or autothermic reforming is a known process. These gas mixtures (reformates) contain 1 to 40 vol % carbon monoxide, depending on the method that is used.
- To use the reformate as fuel in fuel cells, it is necessary to reduce the carbon monoxide contained in them as far as possible, in order to avoid poisoning of the platinum-containing anode catalyst of the fuel cell in the oxidation of the hydrogen. In addition, the conversion of carbon monoxide in accordance with reaction equation (1) leads to an increase of the hydrogen content of the reformate and thus to an improvement of the efficiency of the overall process.
- For reasons of size and weight, catalysts for conversion of carbon monoxide with very high activity and selectivity are required for use in motor vehicles. The high space-time yields that can be achieved by this allow the volume of the reactors that are required to be kept small.
- The known catalysts for the conversion of carbon monoxide have chiefly been developed for stationary industrial applications. The emphasis lay in the production of pure hydrogen, ammonia and other large scale products that are based on the use of synthesis gas mixtures (CO/H2). Catalysts for the conversion of carbon monoxide in accordance with reaction equation (1) are also called shift catalysts herein.
- These known catalysts are complete catalysts that contain non-noble metals. They are used in two-stage processes. In the first process stage a so-called high temperature CO conversion (high temperature water-gas shift, HTS) is carried out on Fe/Cr catalysts at temperatures between 360 and 450° C. In the subsequent second stage a low-temperature CO conversion (low temperature water-gas shift, LTS) is undertaken on Cu/ZnO catalysts at temperatures between 200 and 270° C. After the low temperature process stage carbon monoxide concentrations of less than 1 vol % in correspondence with the thermal equilibrium are obtained.
- The conventional catalysts for the conversion of carbon monoxide have crucial disadvantages:
- The described two stage conduct of the process is necessary because of the properties of these catalysts. While Cu/ZnO-containing catalysts become deactivated above 270° C. because of recrystallization, or sintering, of the copper, the Fe/Cr-containing catalysts that are used in the high temperature range cannot be used at low temperatures because of insufficient activity. If the indicated temperature range of the high temperature catalysts is exceeded, methanation reactions (reaction equations (2) and (3)) can occur, which reduce the selectivity of the high temperature catalyst and because of this lower the overall efficiency of the hydrogen generation system.
- Both the known high-temperature and the low-temperature catalysts are bulk catalysts, in which the catalyst material is pressed to form pellets or other molded bodies. Accordingly, they consist entirely of catalytically active mass and are also called complete catalysts. As a rule, they have a very high bulk weight.
- The known industrial methods for conversion of carbon monoxide on catalysts according to reaction equation (1) operate at space velocities of the gas mixture between 300 and 3000 h−1. These low velocities are not sufficient for use in motor vehicles.
-
- The known Cu/ZnO and Fe/Cr catalysts have to be activated by reduction before they are used. The activated catalysts are sensitive to oxygen. Upon contact with atmospheric oxygen they are reoxidized and deactivated in an exothermic reaction.
- In comparison with the just described industrial high temperature and low temperature catalysts based on Fe/Cr or Cu/ZnO, noble metal catalysts for these uses are also known, mainly from the scientific literature.
- D. C. Grenoble et al. describe in “The Chemistry and Catalysis of the Water Gas Shift Reaction. 1. The Kinetics over Supported Metal Catalysts,” J. Catal. 67 (1980) 90-102, powdered catalysts that contain Cu, Re, Co, Ru, Ni, Pt, Os, Au, Fe, Pd, Rh or Ir as active components and that are deposited on aluminum oxide (Al2O3) as a support material. The kinetic tests gave a reaction order of about 0.2 for carbon monoxide and about 0.5 for the water that was used.
- In “Methanization and Water Gas Shift Reactions over Pt/CeO2,” J. Catal. 96 (1985), 285-287, Steinberg et al. observed poor selectivities in view of the carbon monoxide conversion according to reaction equation (1). Accordingly, the product gas mixture contains high proportions of methane.
- In “Water gas shift conversion using a feed with a low steam to carbon monoxide ratio and containing sulfur,” Catal. Today 30 (1996) 107-118, J. Ross et al. investigate a Pt/ZrO2 catalyst, in addition to Fe/Cr, Cu/ZnO and Co/Cr catalysts. This catalyst shows a carbon monoxide conversion of 50% at 320° C. The Pt/ZrO2 catalyst shows the highest tolerance for sulfur-containing compounds among the tested compounds. It shows a conversion of 25% at 300° C. and a conversion of 70% at 350° C. This corresponds to a specific carbon monoxide conversion rate RCO (300° C.)=7.00×10−6 mol/(gcat·sec), or RCO (350° C.)=1.95×10−5 mol/(gcat·sec).
- FR 2567866 A describes a copper- and/or palladium-containing catalyst on a support of ZnAl2O4 spinel, which is obtained by impregnating the spinel formed into particles with diameters between 0.4 and 0.6 mm with solutions of copper and/or palladium and calcining it. A conversion of 86% is achieved with this catalyst at pressures of 40 bar and a temperature of 250° C. at a very high excess of water (H2O/CO=10).
- The powdered catalyst systems that have been investigated in the scientific literature are not suitable for industrial use.
- The known complete catalysts in the form of tablets, pellets or irregularly shaped particles are used as so called bulk catalysts. Only unsatisfactory space-time yields are obtained with such catalysts. In addition, the achievable specific conversion rates with these catalysts are low.
- Accordingly, an object of the present invention is to provide a method for conversion of carbon monoxide in a hydrogen-containing gas mixture that, under the conditions of mobile use in motor vehicles with their rapidly changing power requirements, a high specific conversion rate for carbon monoxide with good selectivity, has high temperature stability and is insensitive to oxygen in the educt gas mixture.
- This above and other objects of the invention can be achieved by a method for catalytic conversion of carbon monoxide to carbon dioxide and hydrogen (carbon monoxide conversion) in a hydrogen-containing gas mixture. For conversion of the carbon monoxide, the gas mixture is passed over a shift catalyst, which is at the operating temperature for carbon monoxide conversion. The method features a shift catalyst based on noble metals that is applied to an inert carrier in the form of a coating.
- The method of the present invention is specifically directed to mobile use in motor vehicles powered by fuel cells in order to effectively removed carbon monoxide from the hydrogen-rich gas mixture that is obtained by steam reforming, partial oxidation or autothermic reforming (hereinafter also called reformate gas) under all conditions of operation of the motor vehicle. The gas mixture can contain up to 40 vol % carbon monoxide, depending on its production.
- The mobile use of the method imposes high requirements on its efficiency and dynamics. During the operation of the motor vehicle, the catalysts are loaded with very different space velocities. They vary between a low space velocity at idling and 100,000 h−1 at full load.
- The method of the invention enables a high efficiency, i.e., a high space-time yield through the application of the catalyst in the form of a coating onto an inert carrier. Such a catalyst is also called a coating catalyst herein. The monolithic honeycomb elements of ceramic or metal with cell densities (number of flow channels per area of cross section) of more than 10 cm−2 that are known from auto exhaust treatment are suitable as carrier. However, metal sheet, heat exchanger plates, open-cell ceramic or metal foam elements and irregularly shaped elements formed in each case according to requirements can also be used as carriers. The thickness of the coating can vary between 10 and 100 μm according to application.
- A carrier within the scope of this invention is characterized as inert if the material of the carrier does not participate or participates only negligibly in the catalytic conversion. As a rule, these are bodies with low specific surface and low porosity.
- A catalyst that contains the elements of the platinum group of metals, thus platinum, palladium, rhodium, iridium, ruthenium and osmium, or gold as the catalytic active components on an oxide support made from the group consisting of aluminum oxide, silicon dioxide, titanium oxide, rare earth oxides or mixed oxides of these or zeolites is suitable for the proposed method. In order to enable distribution of the catalytically active components on the support material that is as fine as possible, the support material should have at least a specific surface (BET surface, measured in accordance with DIN 66132) of more than 10 m2/g.
- This noble metal catalyst exhibits a shift activity, i.e., it is capable, if the appropriate reaction conditions exist (temperature, gas composition), of converting carbon monoxide with water in accordance with reaction equation (1) to carbon dioxide and hydrogen. For this reason it is also called a noble metal shift catalyst herein. Its shift activity and selectivity can be improved by the addition of other catalytically active components, or promoters. Among these are elements of the rare earth metals, in particular cerium and lanthanum, as well as the non-noble metals of the subgroups of the periodic system of elements, especially iron or copper.
- The shift activity and selectivity can, moreover, also be increased by doping the support material with redox-active oxides of the metals cerium, zirconium, titanium, vanadium, manganese and iron in an amount of 1 to 50 wt % with respect to the total weight of the support material.
- A preferred shift catalyst for the method in accordance with the invention contains platinum and/or palladium together with iron or copper as well as cerium oxide on a finely divided aluminum oxide.
- The use of the shift catalyst based on noble metals for the method also has the advantage that this catalyst does not become deactivated by contact with oxygen. For this reason no costly measures to protect the catalyst from contact with air are necessary in a motor vehicle.
- The present invention will now be described in further detail.
- In accordance with the invention, the described catalyst material is not processed to complete catalysts, but rather is applied in the form of a coating to inert supports. In this way the disadvantages of complete catalysts that consist of the catalytically active centers in the interior of the complete catalyst being poorly accessible to the reactants are avoided in this method. Poor accessibility reduces the specific conversion rate for carbon monoxide and thus the achievable space-time yield. This has the corresponding negative effects on the volume of the required reactor. The vibrations caused by operation of the motor vehicle additionally lead to undesired abrasion of complete catalysts, which blocks the flow paths in the catalyst bed and thus continuously increases the pressure difference in the reactor.
- The process operates at gas mixture space velocities from idling space velocity up to a value of 100,000 h−1 and at a pressure between atmospheric pressure and 10 bar, where the space velocity is given in reference to the volume of carrier coated with the catalyst. The method can be used both for low-temperature CO conversion as well a for high-temperature CO conversion.
- A noble metal shift catalyst with an operating temperature between 180 and 300° C. is used for the low-temperature CO conversion. The low operating temperature is achieved through a relatively high charge of catalytically active noble metals on the catalyst. In low-temperature CO conversion the reformate gas usually contains 2 to 15 vol % carbon monoxide and has an input temperature between 100 and 250° C. which results from the reforming process.
- A noble metal shift catalyst with an operating temperature between 280 and 550° C. is used for the high temperature CO conversion. In the high temperature CO conversion the reformate gas usually contains 2 to 40 vol % carbon monoxide and has an input temperature between 300 and 600° C., which results from the reforming process.
- The method also allows a high temperature conversion stage and a low temperature conversion stage to be connected in succession. The gas mixture in this case leaves the high temperature stage at a temperature that corresponds to the operating temperature of the catalyst of the high temperature stage and for this reason has to be cooled to the operating temperature of the catalyst of the low-temperature stage before contact with it.
- There are various possibilities for production of a coating catalyst suitable for the method, a few of which are discussed here.
- To produce a shift catalyst on a carrier element in accordance with the invention, the support material for the catalytically active components can be suspended in an aqueous solution of soluble compounds of a noble metal selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, osmium, gold and mixtures thereof and other soluble compounds of non-noble metals of the subgroups. Then the acid suspension is neutralized at elevated temperature with a base, for example, a sodium carbonate, and then reduced at the same temperature with an aqueous reducing agent (formaldehyde, hydrazine), filtered, washed, dried, calcined in an oxidizing atmosphere at temperatures between 300 and 550° C., and then reduced at temperatures between 300 and 600° C. The catalyst material is again suspended in water to produce a coating suspension. The carrier element is coated with this suspension. For this, the methods for coating carrier elements that are known from auto exhaust catalysis can be used. To finish the production of the coating catalyst the coating is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
- As an alternative to the described method, the carrier element is first coated only with the support material, where the support material can contain rare earth oxides and oxides of non-noble metals of the subgroups. The coating on the carrier element is then impregnated with a solution of at least one soluble noble metal compound, soluble compounds of the rare earths and the non-noble metals of the subgroups. To finish the production of the coating catalyst, the coated carrier element is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
- Another variation for making a coating catalyst in accordance with the invention resides in first producing a suspension of the support material, the soluble compounds of the noble metals and optionally the soluble compounds of the non-noble metals of the subgroups and the rare earths. The dissolved components of the suspension are then precipitated onto the suspended support material through the addition of a basic precipitation agent such as sodium hydroxide. The suspension prepared in this way is used directly for coating the carrier element. To finish the production of the coating catalyst, the coated carrier element is dried, calcined at temperatures between 300 and 600° C. and reduced in a hydrogen-containing gas at temperatures between 300 and 600° C.
- The invention is illustrated in more detail by means of the following examples.
- A noble metal shift catalyst (catalyst A) was produced as follows:
- A ceramic element honeycomb carrier with 93 cells per square centimeter and a volume of 0.041 L was coated with 7.25 g γ-aluminum oxide by immersing it in an aqueous suspension of γ-aluminum oxide (specific surface 140 m2/g) and calcining for 2 h at 600° C. After calcination the coated honeycomb element was impregnated with a solution of Ce(NO3)2.6H2O and then calcined for 2 h at 500° C. The calcined molded element was then impregnated with a solution of Pt(NO3)2, Pd(NO3)2 and Fe(NO3)3.
- The catalytically active coating of the catalyst prepared in this way had a total weight of 5.16 g, which corresponds to 126 g per liter of volume of the honeycomb element. It contained 1.2 wt % Pt, 1.2 wt % Pd, 2.4 wt % Fe, 35.7 wt % CeO2 and 59.5 wt % Al2O3.
- The catalyst was tested under the conditions of a high temperature conversion with a synthetic reformate. Its CO2 selectivity SCO2, CO conversion, as well as specific conversion rate RCO in accordance with equation (4) were measured. The following gas composition was used for the high temperature conversion: 27.0 vol % H2, 9.0 vol % CO, 9.0 vol % CO2, 18.0 vol % HO, 37.0 vol % N2. The catalysts were tested at a gas space velocity GHSV=10,000 h−1 and a pressure of 2 bar (absolute).
-
-
- As Tables 1 and 2 show, both catalysts exhibit comparable CO conversions. However, catalyst A in accordance with the invention shows a tenfold higher specific conversion rate RCO in comparison with catalyst B, because of its higher activity.
- Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto.
- German priority application 100 13 895.0 is relied on and incorporated herein by reference.
Claims (13)
1. A method for the catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture with water to form carbon dioxide and hydrogen comprising passing said gas mixture over a shift catalyst, which is at an operating temperature for the carbon monoxide conversion, said shift catalyst being at least one noble metal that is applied to an inert support in the form of a coating.
2. The method according to claim 1 , wherein the shift catalyst contains at least one of the noble metals platinum, palladium, rhodium, ruthenium, iridium, osmium and gold on an oxide support material selected from the group and consisting of aluminum oxide, silicon dioxide, titanium dioxide, rare earth oxides, mixed oxides thereof and zeolites.
3. The method according to claim 2 , wherein the shift catalyst contains at least one rare earth metal as an additional catalytically active component.
4. The method according to claim 2 , wherein the shift catalyst contains at least one non-noble metal of the subgroups of the periodic system of elements as an additional catalytically active component.
5. The method according to claim 4 , wherein the oxide support material is doped with a redox-active oxide of a metal selected from the group consisting of cerium, zirconium, titanium, vanadium, manganese and iron in an amount of 1 to 50 wt % with respect to the total weight of the support material.
6. The method according to claim 5 , wherein the shift catalyst contains platinum and/or palladium together with iron or copper as well as cerium oxide on finely divided aluminum oxide.
7. The method according to claim 1 , wherein a honeycomb element of ceramic or metal, open-cell, ceramic or metallic foam elements, metal sheet, heat exchanger plates or irregularly shaped elements is a carrier.
8. The method according to claim 7 , further comprising passing the gas mixture over the catalyst at a space velocity between an idling space velocity and 100,000 h−1 and at a pressure between atmospheric pressure and 10 bar, where the space velocity refers to the volume of the carrier coated with the catalyst.
9. The method according to claim 8 , wherein the temperature of the shift catalyst lies between 180 and 300° C.
10. The method according to claim 9 , wherein the gas mixture contains 2 to 15 vol % carbon monoxide.
11. The method according to claim 8 , wherein the operating temperature of the shift catalyst lies between 280 and 550° C.
12. The method according to claim 8 , wherein the shift catalyst with an operating temperature between 280 and 550° C. is another shift catalyst with an operating temperature between 180 and 300° C. and that the gas mixture is cooled to the operating temperature of the additional catalyst before contact with it.
13. The method according to claim 11 , wherein the gas mixture contains 2 to 40 vol % carbon monoxide.
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DE10013895.0 | 2000-03-21 | ||
US09/568,814 US6723298B1 (en) | 2000-03-21 | 2000-05-11 | Method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture |
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US20020147103A1 (en) * | 2000-09-25 | 2002-10-10 | Ruettinger Wolfgang F. | Enhanced stability water-gas shift reaction catalysts |
US20040221508A1 (en) * | 2002-05-21 | 2004-11-11 | Conoco Inc. | Rare earth aluminates and gallates supported rhodium catalysts for catalytic partial oxidation of hydrocarbons |
US7001867B2 (en) * | 2002-05-21 | 2006-02-21 | Conocophillips Company | Rare earth aluminates and gallates supported rhodium catalysts for catalytic partial oxidation of hydrocarbons |
US20060194694A1 (en) * | 2002-12-20 | 2006-08-31 | Honda Giken Kogyo Kabushiki Kaisha | Platinum-ruthenium containing catalyst formulations for hydrogen generation |
US8003565B2 (en) * | 2002-12-20 | 2011-08-23 | Honda Giken Kogyo Kabushiki Kaisha | Platinum-ruthenium containing catalyst formulations for hydrogen generation |
US20070253893A1 (en) * | 2006-04-26 | 2007-11-01 | Dagle Robert A | Selective CO methanation catalysis |
US8877674B2 (en) * | 2006-04-26 | 2014-11-04 | Battelle Memorial Institute | Selective CO methanation catalysis |
US10351779B2 (en) * | 2015-03-31 | 2019-07-16 | Johnson Matthey Public Limited Company | Catalyst precursor, method of preparation and use thereof |
WO2018095882A1 (en) | 2016-11-22 | 2018-05-31 | Umicore Ag & Co. Kg | Iron containing catalyst |
Also Published As
Publication number | Publication date |
---|---|
ES2319502T3 (en) | 2009-05-08 |
EP1136441A2 (en) | 2001-09-26 |
EP1136441A3 (en) | 2002-08-21 |
BR0101098A (en) | 2001-11-06 |
DK1136441T3 (en) | 2009-04-14 |
JP2001316682A (en) | 2001-11-16 |
KR100818900B1 (en) | 2008-04-04 |
JP4819235B2 (en) | 2011-11-24 |
ATE421379T1 (en) | 2009-02-15 |
CA2341056A1 (en) | 2001-09-21 |
DE10013895A1 (en) | 2001-10-04 |
EP1136441B1 (en) | 2009-01-21 |
US6723298B1 (en) | 2004-04-20 |
DE50114668D1 (en) | 2009-03-12 |
KR20010092399A (en) | 2001-10-24 |
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