CA2142781A1 - Hydrocarbon reforming catalyst material and configuration of the same - Google Patents
Hydrocarbon reforming catalyst material and configuration of the sameInfo
- Publication number
- CA2142781A1 CA2142781A1 CA002142781A CA2142781A CA2142781A1 CA 2142781 A1 CA2142781 A1 CA 2142781A1 CA 002142781 A CA002142781 A CA 002142781A CA 2142781 A CA2142781 A CA 2142781A CA 2142781 A1 CA2142781 A1 CA 2142781A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- reforming
- catalyst support
- hydrocarbon
- reforming catalyst
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 351
- 238000002407 reforming Methods 0.000 title claims abstract description 220
- 239000000463 material Substances 0.000 title claims abstract description 133
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 110
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 110
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 106
- 239000000446 fuel Substances 0.000 claims abstract description 115
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000002915 spent fuel radioactive waste Substances 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 29
- 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 26
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000008188 pellet Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 112
- 239000002737 fuel gas Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 43
- 229910052799 carbon Inorganic materials 0.000 description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 230000003197 catalytic effect Effects 0.000 description 24
- 230000008021 deposition Effects 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000005755 formation reaction Methods 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 14
- 239000000395 magnesium oxide Substances 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 238000006057 reforming reaction Methods 0.000 description 10
- 230000002035 prolonged effect Effects 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 229910001026 inconel Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000010410 dusting Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 propal1e Chemical compound 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002084 calcia-stabilized zirconia Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010338 mechanical breakdown Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/56—
-
- 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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- 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
Abstract
A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in anelectrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall.
Description
- 1 - 56,013 HYDROCARBON REFORMING CATALYST MATERIAL AND
CONFIGURATION OF THE SAME
Government Contract The Government of the United States of America has rights in the invention pursuant to Cooperative Agreement DE-AC21-80ET-17089 awarded by the United States Department of Energy.
5Back~round of the Invention 1. Field of the Invention The invention relates to the field of catalytic hydrocarbon gas reformers, and to an improved catalyst support material and catalyst support configuration for use in a catalytic hydrocarbon gas reformer. The invention is particularly useful in high 10 temperature, solid oxide electrolyte electrochemical gel~el~ols for electrical power gelle,~lion. More particularly, one aspect of the invention is directed to a reforming catalyst support comprising a porous, non-rigid fibrous material having improved~imPn~ional stability during prolonged operation, and another aspect of the invention is directed to a reforming catalyst support mounted in a configuration defining discrete 15 flow paths along the length of the catalyst support, for improved heat transfer rate and csi~ e to pressure drop across the reformable hydrocarbon gas flow paths.
Natural gases comprising methane, ethane, propal1e, butane and/or nitrogen and the like, vaporized petroleum fractions such as naphtha and the like, and also alcohols, for example ethyl alcohol and the like, are applopliate fuels for electrochemical 20 reactions, and can be con~llmecl in an electroch~mir-~l generator apparatus for gelle~lhlg electrical power, for example, a high temperature, solid oxide ~ 2142781 - 2 - 56,013 electrochemical fuel cell generator. However, the direct use of hydrocarbon fuels for generating electrical power can cause carbon deposition or the formation of soot on the electrochemical fuel cells of the generator and other generator components, at least partly from hydrocarbon cracking. Deposition of carbon on the electrochemical 5 generator components, for example, insulation boards, fuel distribution boards, support blocks, partition boards and fuel cells, reduces the efficiency of the electrochemical generator, inter alia, by blocking transport paths, providing electrical short-circuit paths and reducing insulation effects.
To reduce carbon deposition, it is known to reform the hydrocarbon feed fuel 10 gas entering the fuel cell chamber of an electrochemical generator apparatus into simpler molecules, especially into carbon monoxide (CO) and hydrogen (H2), through the use of a reforming catalyst. Hydrocarbon reforming is therefore used to provide low carbonizing fuels for the electroch~-n ir~l cells. It is also known that the presence of water vapor (H20,g,) and/or carbon dioxide (CO2) and a reforming catalyst allows 15 for the direct conversion of gaseous hydrocarbons, such as natural gas, to CO and H2 by an endothermic reforming reaction, i.e., requiring a supply of heat. The reforming reaction is best performed at a lenlpel~lulc of about 900C.
The reformed hydrocarbon fuel is then combined, for example, in an electrochemical generator appalalus, along with an oxidant such as air, to produce heat 20 and electric power. Since the reforming reaction is endothermic, additional thermal energy must be supplied, eg., by direct combustion or by heat transfer through the walls of a heat exchanger, such as in a steam-air or air-air heat exchanger. Typically, the heat required for the reforming reaction in an electrochemical generator apparatus is derived from a si~nifi~nt fraction of the excess heat that results from operation of 25 the electrochemical generator.
High temperature, solid oxide electrolyte fuel cells and multi-cell generators and configurations clesignP~l for converting chemical energy into direct current electrical energy, typically in the temperature range of from 600C to 1200C, are well known and taught, for example, in U.S. Patent Nos. 4,395,468 (Isenberg) and 4,490,444 30 (Isenberg). A multi-cell generator generally contains a plurality of parallel elongated, electri~lly interconnected, tubular, electrochemical fuel cells, each fuel cell having an - 21~278 ~
CONFIGURATION OF THE SAME
Government Contract The Government of the United States of America has rights in the invention pursuant to Cooperative Agreement DE-AC21-80ET-17089 awarded by the United States Department of Energy.
5Back~round of the Invention 1. Field of the Invention The invention relates to the field of catalytic hydrocarbon gas reformers, and to an improved catalyst support material and catalyst support configuration for use in a catalytic hydrocarbon gas reformer. The invention is particularly useful in high 10 temperature, solid oxide electrolyte electrochemical gel~el~ols for electrical power gelle,~lion. More particularly, one aspect of the invention is directed to a reforming catalyst support comprising a porous, non-rigid fibrous material having improved~imPn~ional stability during prolonged operation, and another aspect of the invention is directed to a reforming catalyst support mounted in a configuration defining discrete 15 flow paths along the length of the catalyst support, for improved heat transfer rate and csi~ e to pressure drop across the reformable hydrocarbon gas flow paths.
Natural gases comprising methane, ethane, propal1e, butane and/or nitrogen and the like, vaporized petroleum fractions such as naphtha and the like, and also alcohols, for example ethyl alcohol and the like, are applopliate fuels for electrochemical 20 reactions, and can be con~llmecl in an electroch~mir-~l generator apparatus for gelle~lhlg electrical power, for example, a high temperature, solid oxide ~ 2142781 - 2 - 56,013 electrochemical fuel cell generator. However, the direct use of hydrocarbon fuels for generating electrical power can cause carbon deposition or the formation of soot on the electrochemical fuel cells of the generator and other generator components, at least partly from hydrocarbon cracking. Deposition of carbon on the electrochemical 5 generator components, for example, insulation boards, fuel distribution boards, support blocks, partition boards and fuel cells, reduces the efficiency of the electrochemical generator, inter alia, by blocking transport paths, providing electrical short-circuit paths and reducing insulation effects.
To reduce carbon deposition, it is known to reform the hydrocarbon feed fuel 10 gas entering the fuel cell chamber of an electrochemical generator apparatus into simpler molecules, especially into carbon monoxide (CO) and hydrogen (H2), through the use of a reforming catalyst. Hydrocarbon reforming is therefore used to provide low carbonizing fuels for the electroch~-n ir~l cells. It is also known that the presence of water vapor (H20,g,) and/or carbon dioxide (CO2) and a reforming catalyst allows 15 for the direct conversion of gaseous hydrocarbons, such as natural gas, to CO and H2 by an endothermic reforming reaction, i.e., requiring a supply of heat. The reforming reaction is best performed at a lenlpel~lulc of about 900C.
The reformed hydrocarbon fuel is then combined, for example, in an electrochemical generator appalalus, along with an oxidant such as air, to produce heat 20 and electric power. Since the reforming reaction is endothermic, additional thermal energy must be supplied, eg., by direct combustion or by heat transfer through the walls of a heat exchanger, such as in a steam-air or air-air heat exchanger. Typically, the heat required for the reforming reaction in an electrochemical generator apparatus is derived from a si~nifi~nt fraction of the excess heat that results from operation of 25 the electrochemical generator.
High temperature, solid oxide electrolyte fuel cells and multi-cell generators and configurations clesignP~l for converting chemical energy into direct current electrical energy, typically in the temperature range of from 600C to 1200C, are well known and taught, for example, in U.S. Patent Nos. 4,395,468 (Isenberg) and 4,490,444 30 (Isenberg). A multi-cell generator generally contains a plurality of parallel elongated, electri~lly interconnected, tubular, electrochemical fuel cells, each fuel cell having an - 21~278 ~
- 3 - 56,013 exterior fuel electrode, an interior air electrode, a solid oxide electrolyte sandwiched between the electrodes, and means for entry of a gaseous oxidant and a gaseous hydrocarbon feed fuel. A previously reformed hydrocarbon feed fuel, i.e., converted to H2 and CO, is fed into the generator at one end and flows parallel to the exterior of 5 a fuel electrode surface that is elongated along an axis. The fuel is oxidized by an oxidant, such as oxygen or air, which is fed into the generator at another end and parallel to the interior of the air electrode surface that is elongated along an axis.
Direct current electrical energy is generated. Spent fuel is combusted with spent oxidant in a separate combustion chamber and is vented from the generator as a hot 10 combusted exhaust gas.
In the known high telllpeldlul~, solid oxide electrolyte fuel cells and multi-cell generators, the hydrocarbon feed fuel gas, such as natuMl gas, is generally mixed with water vapor and/or carbon dioxide, typically supplied from a recirculated spent fuel gas (unoxidized) typically cont~ining H2O and CO2, and is reformed as an initial step, i.e., 15 converted to H2 and CO, through the use of a reforming catalyst, typically nickel or pl~tinllm, supported on a catalyst support material, typically rigid and highly sintered ~lllmin~ pellets. Reforming the hydrocarbon feed fuel can be performed either inside or outside the electroch~mi-~l generator. However, hydrocarbon reforming outside of the electrochemical generator is less desirable in that heat energy is lost at the reformer 20 and at the co,~ clil~g conduits, making such a system more e~ensi~e and complicated than one with an internal reformer. Moreover, the hydrocarbon reforming reactionis ~lro,llled at a temperature close to that of the electrochemical fuel cell operation.
Accordi~ly, reforming efficiency is best where the reformer is inside the electroch.orni~l generator and the largest possible fraction of excess heat that results 25 from the fuel cell generator operation can be usefully applied.
U.S. Patent No. 4,729,931 (Grimble) discloses a fuel cell generator having an internal catalytic hydrocarbon reformer where hot spent fuel gas cont~ining H2O and CO2 is recirculated and drawn into fresh hydrocarbon feed fuel at an ejector nozzle, and the reformable gaseous mixture is then fed through an internal hydrocarbon 30 reforming chamber cont~ining a packed reforming catalyst bed or packed column of finely divided Ni and Pt, disposed alongside the length of the fuel cell chamber.
21~27~1 4- 56,013 After flowing through the packed bed at about 900C, the reformable gaseous mixture yields a reformed fuel gas, namely H2 and CO, which is ultimately fed across the fuel - electrodes in the fuel cell chamber. The use, however, of not easily monitored or controlled amounts of recirculated spent fuel gas as a source of H2O and/or CO2 5 combined with fresh hydrocarbon feed fuel for the reforming reaction has a potential to result in several problems due to carbon deposition on the reforming catalyst during hydrocarbon reforming and other also on generator components. Carbon deposition on the internally located reforming catalyst and catalyst support structure can result in blocked flow paths across a catalyst bed, thereby increasing the pressure drop across 10 the bed. It can also result in increased internal stresses in catalyst support structures which are conventionally porous, rigid, sintered, alumina pellets impregnated with a reforming catalyst, thereby causing pulverization and cracking of the catalyst support structure and reducing its reforming efficiency.
Carbon deposition on a hydrocarbon reforming catalyst surface is thought to 15 result from insufficient adsorption of H2O and/or CO2 on the reforming catalyst surface, i.e., insufficient presence of the oxygen species. R~ cecl gasification of carbon from the adsorbed hydrocarbon feed gas, and hydrocarbon cracking, are theresults. The oxygen species is needed in sufficient quantity to react with the adsorbed carbon species to form carbon monoxide. Without oxygen, carbon is formed on the 20 reforming catalyst and on other components of the electrochemical generator. This resl-lting deposited carbon is encapsulating in nature and is resistant to oxidation by H2O present in the reforming atmosphere.
There have been atle~ )ts made to reduce carbon deposition on the hydrocarbon reforming catalyst and other electrochemical fuel cell generator col~ol~ell~. In order 25 to reduce carbon deposition on the lefo~ lg catalyst and reforming catalyst support structure, it is known to reform hydrocarbon feed fuel gas in an excess of water vapor and/or carbon dioxide in the presence of reforming catalyst.
U.S. Patent No. 5,143,800 (George et al.) discloses a high temperature, solid oxide electrolyte fuel cell generator having an internal catalytic hydrocarbon reformer 30 where spent fuel cont~ining H2O and CO2 is recirculated and aspirated into fresh feed hydrocarbon fuel at a circulation or mixing nozzle prior to entering the reforming ` 21427~1 - 5 - 56,013 chamber, and characterized in that the fresh feed inlet has a by-pass channel into the spent recirculated fuel channel having valving to control the spent fuel inclusion in the fresh hydrocarbon feed fuel prior to entering a reforming chamber cont~ining a nickel catalyst. Additional spent fuel is combined with spent oxidant in a combustion 5 chamber to form combusted exhaust gas that is circulated to heat the reformingchamber and other components of the fuel cell. The valve adjusted combination ofspent fuel with fresh feed fuel attempts to prevent carbon deposition and soot formation within the reforming catalyst and reforming catalyst support structure and other fuel cell generator components.
Other attempts have been made to reduce carbon deposition on the hydrocarbon reforming catalyst and the reforming catalyst support structure. U.S. Patent No.5,169,730 (Reichner et al.) discloses a high temperature, solid oxide fuel cell having an internal catalytic hydrocarbon reformer where the recirculated spent fuel is cooled through heat transfer operations with other components of the fuel cell generator to a 15 temperature of below 400C prior to entering the nozzle or ejector located at a low temperature exterior position to the main body of the generator, and then mixing with the fresh hydrocarbon feed fuel to avoid hydrocarbon cracking at the nozzle and deactivation or poisoning of the reforming catalyst.
U.S. Patent 4,898,792 (Singh et al.) discloses a high temperature, solid oxide electrolyte fuel cell generator having porous, fuel conditioner boards used to distribute a hydrocarbon fuel over the fuel cells and also to act in a hydrocarbon reforming capacity. In Singh et al., the reforming catalyst material used to reduce carbonformation includes a porous, rigid pressed or sintered felt of powder or fiber alumina as a catalyst support structure impregnated or treated with a reforming catalyst25 including catalytic Ni and also metal salts, the salts including nitrates, formates and acet~tto~, and metal oxides, and the metals being selected from the group of Mg, Ca-Al, Sr-Al, Ce, Ba and mixtures thereof. It is known that metal oxides are effective in readily adsorbing gaseous H2O.
In all prior designs, however, during long term reforming operation on hydrocarbon fuels, there remains the possibility of p~,ro"na~ce degradation of the reforming catalyst and reforming catalyst support structure, and also of other 21~2781 - 6 - 56,013 components of a fuel cell generator Although the operation of a reformer, for example, in an electrochemical generator, is intended to take place in a relatively carbon deposition free operating range, prolonged operation could result in carbon formation on the catalyst and catalyst support due to occasional unavoidable variation 5 from nominal opeldlillg parameters, such as, for example, a change in O:C ratios or a change in temperature of the reformer feed gas mixture.
Commercial reforming catalyst materials presently in use for hydrocarbon reforming in high temperature, solid oxide fuel cells typically include a catalyst carrier or support structure, active catalyst deposited or impregnated on the support structure 10 surfaces, and optionally, other promoters. The catalyst support is typically a porous material having high total surface areas (internal and external) to provide highconcentrations of active sites per unit weight of catalyst. The catalyst support is also typically a rigid material which is made to with~t~n-l high pressure operating conditions, i.e., mainly a carryover from the petrochemical industry, even though high 15 pressure designs are generally not needed when used for hydrocarbon reforming in a high lelll~ldlure, solid oxide fuel cell generator applications. The commercial reforming catalyst material typically used in high tel~ dlul~, solid oxide fuel cell generators consists of a porous, rigid, support catalyst made from sintered and/or pressed powdered ~lumin~ (Al2O3), that is impregnated with catalytic Ni and possibly 20 MgO, typically in the form of pellets.
However, these commercial catalyst materials, including a porous, rigid, sintered alumina reforming catalyst support structures doped with catalyst, are prone to mPch~nic~l breakdown, thought to result in part from stresses generated in the rigid, sintered body by carbon formation on the reforrning catalyst material during the25 reforming operation. The meçh~nil~l degradation of the reforming catalyst material, particularly the reforming catalyst support structure reduces the life of the catalyst material and, consequently, degrades the generator electrical output when used in connection with an electroch.omic~l generator. Upon prolonged operation of the reformer, for example, in the electrochrmir~l generator, the reforming catalyst material 30 including the catalyst support and the catalyst deposited thereon are subject to mech~nir~l disintegration, fracturing, dusting and/or pulverization, during carbon 21427~
Direct current electrical energy is generated. Spent fuel is combusted with spent oxidant in a separate combustion chamber and is vented from the generator as a hot 10 combusted exhaust gas.
In the known high telllpeldlul~, solid oxide electrolyte fuel cells and multi-cell generators, the hydrocarbon feed fuel gas, such as natuMl gas, is generally mixed with water vapor and/or carbon dioxide, typically supplied from a recirculated spent fuel gas (unoxidized) typically cont~ining H2O and CO2, and is reformed as an initial step, i.e., 15 converted to H2 and CO, through the use of a reforming catalyst, typically nickel or pl~tinllm, supported on a catalyst support material, typically rigid and highly sintered ~lllmin~ pellets. Reforming the hydrocarbon feed fuel can be performed either inside or outside the electroch~mi-~l generator. However, hydrocarbon reforming outside of the electrochemical generator is less desirable in that heat energy is lost at the reformer 20 and at the co,~ clil~g conduits, making such a system more e~ensi~e and complicated than one with an internal reformer. Moreover, the hydrocarbon reforming reactionis ~lro,llled at a temperature close to that of the electrochemical fuel cell operation.
Accordi~ly, reforming efficiency is best where the reformer is inside the electroch.orni~l generator and the largest possible fraction of excess heat that results 25 from the fuel cell generator operation can be usefully applied.
U.S. Patent No. 4,729,931 (Grimble) discloses a fuel cell generator having an internal catalytic hydrocarbon reformer where hot spent fuel gas cont~ining H2O and CO2 is recirculated and drawn into fresh hydrocarbon feed fuel at an ejector nozzle, and the reformable gaseous mixture is then fed through an internal hydrocarbon 30 reforming chamber cont~ining a packed reforming catalyst bed or packed column of finely divided Ni and Pt, disposed alongside the length of the fuel cell chamber.
21~27~1 4- 56,013 After flowing through the packed bed at about 900C, the reformable gaseous mixture yields a reformed fuel gas, namely H2 and CO, which is ultimately fed across the fuel - electrodes in the fuel cell chamber. The use, however, of not easily monitored or controlled amounts of recirculated spent fuel gas as a source of H2O and/or CO2 5 combined with fresh hydrocarbon feed fuel for the reforming reaction has a potential to result in several problems due to carbon deposition on the reforming catalyst during hydrocarbon reforming and other also on generator components. Carbon deposition on the internally located reforming catalyst and catalyst support structure can result in blocked flow paths across a catalyst bed, thereby increasing the pressure drop across 10 the bed. It can also result in increased internal stresses in catalyst support structures which are conventionally porous, rigid, sintered, alumina pellets impregnated with a reforming catalyst, thereby causing pulverization and cracking of the catalyst support structure and reducing its reforming efficiency.
Carbon deposition on a hydrocarbon reforming catalyst surface is thought to 15 result from insufficient adsorption of H2O and/or CO2 on the reforming catalyst surface, i.e., insufficient presence of the oxygen species. R~ cecl gasification of carbon from the adsorbed hydrocarbon feed gas, and hydrocarbon cracking, are theresults. The oxygen species is needed in sufficient quantity to react with the adsorbed carbon species to form carbon monoxide. Without oxygen, carbon is formed on the 20 reforming catalyst and on other components of the electrochemical generator. This resl-lting deposited carbon is encapsulating in nature and is resistant to oxidation by H2O present in the reforming atmosphere.
There have been atle~ )ts made to reduce carbon deposition on the hydrocarbon reforming catalyst and other electrochemical fuel cell generator col~ol~ell~. In order 25 to reduce carbon deposition on the lefo~ lg catalyst and reforming catalyst support structure, it is known to reform hydrocarbon feed fuel gas in an excess of water vapor and/or carbon dioxide in the presence of reforming catalyst.
U.S. Patent No. 5,143,800 (George et al.) discloses a high temperature, solid oxide electrolyte fuel cell generator having an internal catalytic hydrocarbon reformer 30 where spent fuel cont~ining H2O and CO2 is recirculated and aspirated into fresh feed hydrocarbon fuel at a circulation or mixing nozzle prior to entering the reforming ` 21427~1 - 5 - 56,013 chamber, and characterized in that the fresh feed inlet has a by-pass channel into the spent recirculated fuel channel having valving to control the spent fuel inclusion in the fresh hydrocarbon feed fuel prior to entering a reforming chamber cont~ining a nickel catalyst. Additional spent fuel is combined with spent oxidant in a combustion 5 chamber to form combusted exhaust gas that is circulated to heat the reformingchamber and other components of the fuel cell. The valve adjusted combination ofspent fuel with fresh feed fuel attempts to prevent carbon deposition and soot formation within the reforming catalyst and reforming catalyst support structure and other fuel cell generator components.
Other attempts have been made to reduce carbon deposition on the hydrocarbon reforming catalyst and the reforming catalyst support structure. U.S. Patent No.5,169,730 (Reichner et al.) discloses a high temperature, solid oxide fuel cell having an internal catalytic hydrocarbon reformer where the recirculated spent fuel is cooled through heat transfer operations with other components of the fuel cell generator to a 15 temperature of below 400C prior to entering the nozzle or ejector located at a low temperature exterior position to the main body of the generator, and then mixing with the fresh hydrocarbon feed fuel to avoid hydrocarbon cracking at the nozzle and deactivation or poisoning of the reforming catalyst.
U.S. Patent 4,898,792 (Singh et al.) discloses a high temperature, solid oxide electrolyte fuel cell generator having porous, fuel conditioner boards used to distribute a hydrocarbon fuel over the fuel cells and also to act in a hydrocarbon reforming capacity. In Singh et al., the reforming catalyst material used to reduce carbonformation includes a porous, rigid pressed or sintered felt of powder or fiber alumina as a catalyst support structure impregnated or treated with a reforming catalyst25 including catalytic Ni and also metal salts, the salts including nitrates, formates and acet~tto~, and metal oxides, and the metals being selected from the group of Mg, Ca-Al, Sr-Al, Ce, Ba and mixtures thereof. It is known that metal oxides are effective in readily adsorbing gaseous H2O.
In all prior designs, however, during long term reforming operation on hydrocarbon fuels, there remains the possibility of p~,ro"na~ce degradation of the reforming catalyst and reforming catalyst support structure, and also of other 21~2781 - 6 - 56,013 components of a fuel cell generator Although the operation of a reformer, for example, in an electrochemical generator, is intended to take place in a relatively carbon deposition free operating range, prolonged operation could result in carbon formation on the catalyst and catalyst support due to occasional unavoidable variation 5 from nominal opeldlillg parameters, such as, for example, a change in O:C ratios or a change in temperature of the reformer feed gas mixture.
Commercial reforming catalyst materials presently in use for hydrocarbon reforming in high temperature, solid oxide fuel cells typically include a catalyst carrier or support structure, active catalyst deposited or impregnated on the support structure 10 surfaces, and optionally, other promoters. The catalyst support is typically a porous material having high total surface areas (internal and external) to provide highconcentrations of active sites per unit weight of catalyst. The catalyst support is also typically a rigid material which is made to with~t~n-l high pressure operating conditions, i.e., mainly a carryover from the petrochemical industry, even though high 15 pressure designs are generally not needed when used for hydrocarbon reforming in a high lelll~ldlure, solid oxide fuel cell generator applications. The commercial reforming catalyst material typically used in high tel~ dlul~, solid oxide fuel cell generators consists of a porous, rigid, support catalyst made from sintered and/or pressed powdered ~lumin~ (Al2O3), that is impregnated with catalytic Ni and possibly 20 MgO, typically in the form of pellets.
However, these commercial catalyst materials, including a porous, rigid, sintered alumina reforming catalyst support structures doped with catalyst, are prone to mPch~nic~l breakdown, thought to result in part from stresses generated in the rigid, sintered body by carbon formation on the reforrning catalyst material during the25 reforming operation. The meçh~nil~l degradation of the reforming catalyst material, particularly the reforming catalyst support structure reduces the life of the catalyst material and, consequently, degrades the generator electrical output when used in connection with an electroch.omic~l generator. Upon prolonged operation of the reformer, for example, in the electrochrmir~l generator, the reforming catalyst material 30 including the catalyst support and the catalyst deposited thereon are subject to mech~nir~l disintegration, fracturing, dusting and/or pulverization, during carbon 21427~
- 7 - 56,013 formation which can lead to a pressure buildup across the reformer bed, and, consequently, degradation of the generator electrical output. Moreover, the removal of the carbon, once formed, if needed to regenerate the surface activity of the catalyst by, for example, oxidation, is difficult. There is a need to provide a reforming catalyst 5 material including the catalyst support structure that is not subject to mech~ni~l breakdown and dimensional instability during carbon deposition to provide prolonged catalyst operation, even at lower O:C ratios.
Moreover, commercial reforming catalyst materials typically used in high temperature, solid oxide fuel cell generators typically include catalyst support structures 10 in the form of pellets which are packed in a tubular internal reforming chamber. As described above, the catalyst pellets are typically made from a porous, rigid, sintered alumina support structures which are doped with Ni and possibly MgO. These catalyst pellets can be configured in various shapes, such as spherical, oblate spheroid, annular ("Raschig rings") and wagon wheel shapes. The more complex shapes have relatively 15 greater surface area than simple shapes (~, spheres), but complex shapes havedrawbacks with respect to flow resistance and thermal conductivity through the catalyst bed as well as me~hanical disintegration problems.
These catalyst pellets are further typically contained in a packed arrangement within an elongated reformer tube inside the fuel cell gelle,dtor through which the 20 reformable gas lllixLure stream is passed. These tightly packed catalyst pellets, however, resist gas flow and result in a substantial pressure drop through the catalyst bed. A low pl~,S:iUlC: drop of the reformable gas mixture stream is desirable through the catalyst bed, but is difficult to achieve in a bed comprised of such catalyst pellets.
The pellets have an adverse impact on the l~Çullllable feed gas punl~i~g pressure in the 25 catalytic reformer.
~ n addition, whereas the reforming reactions are endothermic, the pellets detract from heat Lldl~rer from the reformer tube wall toward the center of the catalyst pellet bed. The pellets thus adversely affect the efficiency of the reforming reaction. To compensate, the reformer tube size must be reduced and elongated to provide a smaller 30 cross section, and the overall compactness of the reformer suffers.
Moreover, commercial reforming catalyst materials typically used in high temperature, solid oxide fuel cell generators typically include catalyst support structures 10 in the form of pellets which are packed in a tubular internal reforming chamber. As described above, the catalyst pellets are typically made from a porous, rigid, sintered alumina support structures which are doped with Ni and possibly MgO. These catalyst pellets can be configured in various shapes, such as spherical, oblate spheroid, annular ("Raschig rings") and wagon wheel shapes. The more complex shapes have relatively 15 greater surface area than simple shapes (~, spheres), but complex shapes havedrawbacks with respect to flow resistance and thermal conductivity through the catalyst bed as well as me~hanical disintegration problems.
These catalyst pellets are further typically contained in a packed arrangement within an elongated reformer tube inside the fuel cell gelle,dtor through which the 20 reformable gas lllixLure stream is passed. These tightly packed catalyst pellets, however, resist gas flow and result in a substantial pressure drop through the catalyst bed. A low pl~,S:iUlC: drop of the reformable gas mixture stream is desirable through the catalyst bed, but is difficult to achieve in a bed comprised of such catalyst pellets.
The pellets have an adverse impact on the l~Çullllable feed gas punl~i~g pressure in the 25 catalytic reformer.
~ n addition, whereas the reforming reactions are endothermic, the pellets detract from heat Lldl~rer from the reformer tube wall toward the center of the catalyst pellet bed. The pellets thus adversely affect the efficiency of the reforming reaction. To compensate, the reformer tube size must be reduced and elongated to provide a smaller 30 cross section, and the overall compactness of the reformer suffers.
- 8 - 56,013 Typical hydrocarbon reformer designs consist of a plurality of long, thin tubes filled with these catalyst pellets. Such a reformer design is used to achieve high heat transfer rate while m~int~ining a long gas flow path over a large area of active catalyst.
However, this configuration is not space or volume efficient. Moreover, it results in 5 a relatively high pressure drop of the reformer gas stream through the catalyst bed.
Some proposed hydrocarbon reformer applications are extremely limited in available space allocation and also in pumping pressure available to drive the reformer gas through the catalyst bed. An example is an internal reformer for a high temperature, solid oxide fuel cell recirculation generator incorporating an ejector or nozzle as the 10 gas stream motive element. There is a need for a more optimal configuration of the reforming chamber and the reforming catalyst material contained therein including the catalyst support structure and catalyst deposited thereon, to improve heat transfer rates and resistance to pressure drops.
It would be advantageous for catalytic hydrocarbon reformers, especially in an 15 electrochemical fuel cell generator appaldLus, to contain a reforming catalyst material having a catalyst support structure impregnated with catalyst that is not prone to mechanical or dimensional breakdown due to carbon formation, improves gas streampressure drop through the catalyst bed, and enables a high heat flux to pass from the catalyst cont~inment wall to the lcro"l,able gas stream. According to one aspect of 20 the present invention, a catalyst material is provided including a porous, non-rigid catalyst support material impregnated with a reforming catalyst. The non-rigid, catalyst support is colll~lcssible and improves the stability of the catalyst support against pulverization. Moreover, even in the event of generation operation wherecarbon formation may occasionally become possible, the non-rigid catalyst support of 25 the invention provides structural stability to the catalyst material without pulverization of the catalyst support or the catalyst. According to another aspect of the present invention, a catalyst material is provided including a catalyst support configuration elongated in the direction of reformable gas flow having discrete flow paths or passageways along the catalyst support body to define a reformable gas mixture flow 30 channel or channels therein which provide passageways for the reformable gas mixture at lower plCS~ulc drops and heat transfer rates. The catalyst support configuration, - ~ 214278 1 - 9 - 56,013 therefore, defines discrete passageways along its length for substantial portions of the reformable gas mixture, improving heat transfer properties and reducing the pressure drop and purnping requirements across the catalyst bed.
21~2781 - 10- 56,013 Summary of the Invention It is an object of the invention to provide an electrochemical generator apparatus cont~ining an internal catalytic hydrocarbon reformer including a reforming catalyst material comprising an improved reforming catalyst support material.
5It is another object of the invention to provide a reforming catalyst support material that is non-rigid, flexible and compressible.
It is another object of the invention to provide a reforming catalyst support material having dimensional stability that is not prone to mechanical degradation and pulverization of the catalyst support and catalyst thereon and its support structure 10during prolonged operations.
It is a further object of the invention to provide an electrochf~mi~l generator apparatus cont~ining an internal catalytic hydrocarbon reformer including a reforming catalyst material comprising an illlprov~d reforming catalyst support configuration.
It is yet another object of the invention to provide a reforming catalyst support 15configuration defining flow channels or passageways therein for passage of a lerollllable gas mixture stream that improves heat transfer characteristics and further reduces refollllable gas mixture stream ~,les~ule drops across the catalyst support.
It is a further object of the invention to provide a catalytic hydrocarbon reformer having a reforming catalyst support configuration that is compact.
20It is an advantage of the invention to provide a reforming catalyst material that is not degraded by carbon formation during prolonged use.
It is another advantage of the invention to provide a reforming catalyst material having a low gas stream ~lcs~ule drop through the lerollllillg catalyst support material.
It is another advantage of the invention to provide a lerolllPillg catalyst material 25having a high heat flux between the reforming catalyst support material cont~inment wall and the refo~nable gas mixture stream.
One aspect of the invention resides in a reforming catalyst material comprising a catalyst support illlpregllated with catalyst characterized by the catalyst support being made of a non-rigid, porous, fibrous catalyst support material, wherein the fibers are 30compressible and subst~nti~lly unsinlel~d. The catalyst support is preferably made from ~ min~ and preferably impregnated with catalytic Ni and MgO. The catalyst _ 56,013 support is preferably elongated in the direction of reformable gas flow. The non-rigid and compressible nature of the catalyst support improves dimensional stability during carbon formation in reforming operations.
In another aspect of the invention resides in a reforming catalyst material S configuration characterized by a porous reforming catalyst support impregnated with catalyst, where the catalyst support is elongated in a direction of flow of a reformable hydrocarbon gas, and where a reformable gas conf~rting surface of the catalyst support defines at least one discrete passageway extending along the length of the catalyst support to form a reformable gas flow channel, the at least one discrete passageway being in heat co~ -nication with means for heating the reformable hydrocarbon gas in the at least one discrete passageway. Preferably, the catalyst support is characterized by a plurality of discrete passageways extending along the length of the catalyst support forming a plurality of gas flow channels, where at least one of the gas flow channels carries the reformable hydrocarbon gas. The discrete passageways are preferably formed at least partly by integral slots extending inwardly into the catalyst support and elongated in the direction of gas flow, and there is preferably at least one col~ling wall made from a high telllpelature resistant, thermally conductive material disposed around the catalyst support, where the confining wall partly closes the integral slot. The catalyst support impregnated with catalyst configuration according to the invention configured to define discrete reformable hydrocarbon gas flow channelsimproves reformable hydrocarbon gas stream pres~ure drop through the catalyst bed of the reforming chamber, enables a high heat flux to exist from the catalyst support cont~inm~nt wall to the reformable gas stream disposed in the flow channels, andallows for compactn~oss of design.
Another aspect of the invention resides in an electrochemical generator appalalus, especially a high temperature, solid oxide electrolyte fuel cell generator, comprising; an elongated generator chamber cont~ining at least one cell bundle, the bundle cont~ining a plurality of parallel, elongated electrochemical cells, each cell having an exterior fuel electrode, an interior air electrode, and a solid oxide electrolyte thelcb~lween, a fresh gaseous feed fuel inlet to the generator chamber, a gaseous feed oxidant inlet to the generator chamber, at least one gaseous spent fuel exit from the - 12- 56,013 generator chamber, a combustion chamber, at least one gaseous combusted exhaust exit from the combustion chamber, and, a reforming chamber cont~ining a hydrocarbon reforming catalyst material comprising a catalyst support impregnated with a reforming catalyst, where a spent fuel exit channel passes from the generator chamber to combine 5 with a fresh hydrocarbon feed fuel inlet at a mixing chamber, and a reformablehydrocarbon gas mixture passes from the mixing chamber to the reforming chamber,wherein the reformable hydrocarbon gas mixture is substantially reformed and passes from the reforming chamber into the generator chamber, and, further wherein the a reformable gas contacting surface of the reforming catalyst support impregnated with 10 catalyst comprises at least one discrete passageway formed at least partly integrally in the reforming catalyst support and ext~n-ling along the length of the reforming catalyst support in the direction of reformable hydrocarbon gas flow forming a reformable gas flow channel, the at least one discrete passageway being in heat comm--ni~-~tion with means for heating the reformable hydrocarbon gas in said at least one discrete 15 passageway. Preferably, the reformable gas cont~cting surface of the catalyst support comprises a plurality of discrete passageways disposed adjacent one another in the catalyst support. Preferably, the means for heating said reformable hydrocarbon gas comprises said spent gas exit or combusted exhaust gas exit which is directed in heat co""",l.lir~tion with a wall of the reforming chamber, wherein the wall of the 20 reforming chamber is disposed around the catalyst support, partly closing the at least one discrete passageway. Further, the reforming catalyst material is preferably made of a non-rigid, porous, fibrous catalyst support material, wherein the fibers are c~ essible and subst~nti~lly ul~illL~red, and ill~lcgllatcd with catalytic Ni and MgO.
- 13- 56,013 Brief Description of the Drawin~s There are shown in the drawings certain exemplary embodiments of the invention as presently preferred. It should be understood that the invention is not limited to the embodiments disclosed as examples, and is capable of variation within the scope of the appended claims. In the drawings, FIGURE 1 is a section view along an axial plane, through one embodiment of a high temperature, solid oxide electrolyte electrochemical generator including an internal reforming chamber 56 cont~ining a reforming catalyst material comprising a reforming catalyst support configured according to the invention impregnated with catalyst, shown partly cut away along a direction of axial elongation.
FIGURE 2 is a lateral section view of a monolithic reforming catalyst material c~lllplising a catalyst support arrangement according to an embodiment, showing separate adjacent gas passageways integrally defined within the catalyst support for reducing pressure drop across the catalyst material and for transferring thermal energy from the hot gases to the reformable gases, at least the latter being heated in the presence of a reforming catalyst doped on the catalyst support.
FIGURE 3 is a top view of the catalyst material of FIGURE 2.
FIGURE 4 is a lateral section view of a finned reforming catalyst material including a catalyst support a~ gelllent according to the invention, showing a plurality of comra~t, stackable discs, each disc having sepaldl~ adjacent passageways integrally defined with each catalyst support disc, for reducing pressure drop across the catalyst material and for lldl~llhlg thermal energy from the hot gases to the reformable gases, at least the latter being heated in the presence of a lefoll~ g catalyst doped on the catalyst support.
FIGURE 5 is a top view of the catalyst material of FIGURE 4.
FIGURE 6 is an electron micrograph of a conventional rigid, porous, sintered reforming catalyst support made of alumina, and impl~ dted with Ni catalyst and MgO showing a surface morphology of carbon formed on the surface thereof after operation in a high tem~l~ture, solid oxide electrolyte electrochemical generator similar to the one shown in Figure 1 at 500C in a steam:carbon ratio of 1:1.
- 14- 56,013 FIGURE 7 is an electron micrograph of a catalyst material comprising a non-rigid, porous, fibrous, substantially unsintered, reforming catalyst support material, made from alumina, impregnated with reforming catalyst, Ni and MgO, according tothe invention compared to a prior art rigid, porous, sintered reforming catalyst support, 5 made from alumina, impregnated with reforming catalyst, Ni and~ MgO, after prolonged operation in a high te~eldlul~, solid oxide electrolyte electrochemical generator similar to the one shown in Figure 1 at 500C in a steam:carbon ratio at 1:1.
2142~8 1 - 15- 56,013 Detailed Description of the Preferred Embodiments The term "fuel electrode" as used herein means that electrode in contact with hydrocarbon fuel, the term "air electrode" as used herein means that electrode in contact with air or oxygen. The terms "spent" fuel or "spent" oxidant as used herein 5 refer to partially reacted, low BTU fuel, or partially reacted, depleted oxidant, e.~., cont~ining about 5 to 15% oxygen, respectively. The term "spent" does not include the mixture of the spent fuel combusted with spent oxidant, which mixture is described herein as "combusted exhaust" gas.
Referring to FIGURE 1, an electrochemical apparatus or generator 10 is shown 10 cont~ining cell bundles 12 and 14, each bundle having a plurality of parallel elongated electrochemical fuel cells 16, such as solid oxide electrolyte fuel cells. The fuel cells are located in a generator chamber 22, and can be arranged with the cells or bundles arranged in a rectangular or circular configuration, etc.
Each fuel cell 16 has an exterior fuel electrode 18 covering its elongated 15 surface, shown as a stippled section for the sake of clarity, an interior air electrode, and a solid oxide electrolyte between the electrodes. The air electrode and electrolyte are not shown specifically in FIGURE 1, and can be arranged in a manner that is known in the art.
The air electrode can be a doped ceramic of the perovskite family, for example, 20 doped LaMnO3. The electrolyte can by yttria-stabilized zirconia. The fuel electrode can be a zirconia-nickel cermet material. A calcia stabilized zirconia support for the air electrode can optionally be used. For a detailed description of the materials and construction of an exemplary fuel cell, reference can be made to U.S. Patent No.4,490,444 (Isenberg) and U.S. Patent No. 4,751,152 (Zymboly), which are hereby 25 incorporated by reference.
The electroch~mir~l generator al)pdldlus is intentle~ to operate with an interior temperature in the range of about 600C to about 1200C. An outer housing 20 generally surrounds the electrochemical generator apparatus. The housing is typically comprised of a high leml)eldlule resistant metal such as Inconel or the like. An inner 30 housing (not shown) can ~ulloul1d a plurality of chambers including the generator chamber 22 and a combustion chamber 24. The inner housing, if any, can also 21~2~81 - 16- 56,013 comprise a high temperature resistant metal such as Inconel. Thermal insulation 26, such as low density alumina, preferably is disposed within the outer housing 20.Penclldlulg the housing 20 and insulation 26 are a fresh hydrocarbon feed fuel inlet 28, where the fresh hydrocarbon feed fuel is shown as F, and an oxidant feed 5 inlet 30, where the oxidant such as air is shown as O. Ports can also be provided for electrical leads and the like (not shown).
The generator chamber 22 extends between a wall 32 and a porous barrier 34.
The porous barrier 34 is designed to allow spent fuel gas to exit, as in~ atPd by arrows 36, from the generator chamber 22 to the combustion chamber 24. The 10 generator chamber operates at a lJlCS~Ulc slightly above atmospheric, and thecombustion chamber 24, operates at a slightly lower pres~u,c than the generator chamber. The spent gas 36 combines with spent oxidant, as indicated by arrows 46, forming a hot combusted exhaust gas, as shown as E, which passes through combusted exhaust channel 38.
High tellllJe~dLulc, elongated, solid oxide electrolyte fuel cells 16 extend between the combustion chamber 24 and wall 32 and are disposed in generator chamber 22. The fuel cells 16 have open ends 40 at the combustion chamber 24, and closedends near wall 32, leading to the generator chamber 22. Each individual cell gencldles approximately one volt at nominal loading, and a plurality of cells are electrically interconntocted through conductive felts 42, typically nickel fiber metal. The cells can be connPctPd in a series-parallel array, as described in U.S. Patent 4,395,468 (Isenberg), which is hereby incorporated by lcfclc~lce, to obtain a desired relationship of output voltage to current capacity.
By way of example, during operation of the electro~hl~rnir~l ge~ alor apparatus 10, a gaseous oxidant O, such as air, is fed through oxidant feed inlet 30, and enters oxidant feed conduits 44, for example at a tclllpeldlule of approximately 500C to 700C, and above atmospheric p,cs~uic. The oxidant optionally can be heated prior to entering the housing by conventional means, such as a heat exchanger coupled with a blower. The oxidant in conduits 44 is then passed through the combustion chamber 24, where it is further heated to a telllpcldlulc of approximately 800C to 900C by the combusted e~h~llst gas E. The oxidant then flows through the length of the oxidant ` - 2142781 - 17- 56,013 circuit, through the conduits 44 which extend down the interior length of the fuel cells 16, being further heated to approximately 1000C, by virtue of absorbing most of the heat generated during the electrochemical reaction. A smaller fraction of the heat is absorbed by the fuel.
The oxidant is discharged into the closed end bottom of the fuel cells 16. The oxidant within the fuel cells reverses direction, and electrochemically reacts at the inner air electrode along the inside active length of the fuel cells, being depleted somewhat in oxygen content as it approaches the opposite open end 40 of the fuel cells 16.
The oxidant is reduced at the air electrode-electrolyte interface, supplying oxygen ions which migrate through the electrolyte to the fuel electrode-electrolyte interface where they are oxidized in the presence of reformed hydrocarbon fuel to produce electrons which flow through an external load circuit to the air electrode, thus gelle,aling a flow of electrical current. The electrochemical reactions at the air and fuel electrodes where hydrogen is used as a fuel, for example, are given by the following equations:
2 + 4e~ . 2o2- (air electrode) 202- + 2H2 2H2O + 4e~ (fuel electrode).
A more complete description of the operation of this type of electroch~ al cell can be found in U.S. Patent No. 3,400,054 (Ruka), which is hereby incorporated.
The depleted or spent oxidant is then discharged into the combustion chamber 24 through the open fuel cell ends 40, and is shown as spent oxidant exit streams 46.
The spent oxidant 46 combusts with depleted or spent fuel, part of which passes through porous barrier 34 as shown by arrow 36, to form combusted exhaust gas, which exits the app~lus, for example, through one or more combusted exhaust channels 38, f~ally exiting as the exhaust gas shown as E. The combusted exhaust gas E can be directed to pass in heat l,~rer co~ ni~-~tion with the wall of a reformer prior to exiting the apparatus. The combusted exhaust channels 38 can be made of a high lel~ .alu,e ,~si~la,ll metal, such as Inconel.
214278l - 18- 56,013 In the invention, a gaseous hydrocarbon feed fuel F that has not yet been reformed, such as a gaseous hydrocarbon, including hydrocarbons such as methane,ethane, propane and the like, vaporized petroleum fractions such as naphtha, alcohols such as ethyl alcohol and the like, and/or natural gas, can be fed to the electrochemical S generator apparatus through fresh feed fuel inlet channel 28. For example, a mixture of 85% methane, 10% ethane with a balance of propane, butane and nitrogen, can be fed into the electrochemical generator apparatus through fresh hydrocarbon feed fuel inlet channel 28 and reformed in a reforming chamber 56 into combustible compounds less likely to produce carbon formations and soot on a catalyst material 58 within the 10 reforming chamber 56. The term "catalyst material" as used herein refers to areforming catalyst support material having a reforming catalyst treated, impregnated or doped thereon, and optionally including other promoters or the like.
In the embodiment shown in FIGURE 1, a major portion of the hot, gaseous spent fuel formed along the length of the fuel cells 16 passes to at least one spent fuel 15 recirculation channel 48. Spent fuel recirculation channel 48 likewise can be made of a high temperature resistant metal such as Inconel. Another portion of the hot spent fuel passes into a combustion chamber 24, as previously shown by arrow 36, to combust with spent oxidant, as previously shown by arrow 46, and to preheat the fresh oxidant feed O. The spent fuel recirculation channel 48 cont~ining spent fuel passes 20 from the generator chamber 22 to feed into and combine with the fresh hydrocarbon feed fuel cont~ining feed fuel F at a mixing apparatus 50.
The mixing apparatus S0 can be any known type in the art, for example, an ejector, jet pump, nozzle, aspirator, mixer-nozzle/mixer-diffuser or the like. This allows recirculation of a portion of the spent fuel fed into spent fuel recirculation 25 channel 48 to mix with the fresh hydrocarbon feed fuel F fed through inlet 28 at the mixing apparatus S0 to produce a reformable gas fuel mixture, as shown by arrows 54.
In addition, the mixer optionally can be designed such that the dynamic energy of the fuel mixture at the entrance to the mixer S0, such as a nozzle, is effectively converted to an elevated pressure at an ell~ldnce to a reforming chamber 56 by a diffuser 52, the 30 cross-sectional area of which gets larger as it proceeds from its entrance near the nozzle, to the reforming chamber 56.
- 214!27~1 - 19- 56,013 Prior to passing through the catalytic hydrocarbon reforming chamber 56, the reformable gas fuel mixture 54 generally contains at least H2O vapor (steam), and typically also H2, CO and CO2, all contributed by the spent fuel that enters the mixer apparatus 50 through the spent fuel recirculation channel 48. Preferably, the volume 5 ratio of spent f~el to fresh feed fuel is adjusted by controlling the velocity of the fresh feed fuel input in the mixing apparatus 50 so that approximately two volumes to five volumes of H2O (steam) and CO2 are added to each volume of fresh feed fuel. A
preferred O:C volume ratio is from about 1.2:1 to 3:1 for a natural gas fueled electroch~mi~l fuel cell gellel~tor. The presence of H20,g, and/or CO2 plus a 10 reforming catalyst material allows for the conversion of gaseous hydrocarbons to CO
and H2 and reduces the rate of carbon formation due to hydrocarbon cracking.
The reforming reactions for methane and ethane (natural gas) using water and carbon dioxide, for example, are given by the following equations:
CH4 + H2O CO + 3H2 (1) CH4 + CO2 2CO + 2H2 (2) and, C2H6 + 2H2O 2CO + SH2 (3) C2H6 + 2CO2 4CO + 3H2 (4) The reforming reaction is endothermic and best performed at a temperature of 20 about 900C.
In the embodiment shown in FIGURE 1, the hydrocarbon reformable gaseous fuel mixture 54 next passes from the exit of the mixing apparatus through a catalytic hydrocarbon reforming chamber 56 cont~ining a hydrocarbon reforming catalyst material 58 cartridge comprising a self-supporting catalyst support material that is 25 treated with a reforming catalyst and optionally also treated with promoters or the like.
The reformable gas llli~-tUl`e iS reformed into a relatively low carbonizing fuel, as shown by arrows 64, and exits the reforming chamber into the generator chamber 22 through generator chamber entry ports 66 parallel to the generator chamber 22.
The reforming chamber 56, as shown in FIGURE 1, can contain, for example, 30 a reforming catalyst material 58 having an elongated, cylindrical, catalyst support configuration that defines elongated flow rh~nn~ls or passageways 59 extending through - 2l~27~l - 20 - 56,013 catalyst material 58 positioned in the reforming chamber 56, elongated in the direction of the reformable gas flow path. The channels can be defined in part by annular openings between concentric tubular sections, axial slots, grooves or channels, and/or otherwise formed as explained more fully hereinafter. The reforming chamber 56 can 5 be made of a high temperature resistant metal such as Inconel and configured to accept the reforming catalyst material 58 correspondingly configured therein.
The spent fuel recirculation channel 48 is preferably arranged for th~ lly conductive contact with the means defining the flow channels 59 of the reformingchamber 56, to allow heat transfer between hot spent gas in the recirculation channel 48 and the reformable gases 54 passing through the reforming chamber 56. This arrangement llal~fel~ heat energy from the recirculated spent fuel to provide heat energy needed for the endothermic reforming reaction, which is best perforrned at approximately 900C. Additionally, according to the embodiment in FIGURE 1, the recirculated spent fuel continues in recirculation channel 48 down and around to the 15 mixing nozzle 50 and in contact with the outside of the mixer diffuser chamber 52 with a further transfer of heat energy to the reformable fuel gaseous mixture 54 as it approaches the reforming chamber 56.
The combusted exhaust gas channel 38 can also optionally be arranged for thermal ~ rel to the reforming chamber 56 to provide additional heat to the reformer 20 in a similar ~ . For example, the combusted exhaust gas channel 38 can be arranged to pass through an annular opening between collcellL,ic tubular sections of the r~folllling chamber.
Further, in the embodiment FIGURE 1, the telll~lalure of the spent fuel can be reduced from approximately 1000C at the ~llll~ue to the recirculation fuel channel 25 48 to a suffuiently low lem~l~lure as it approaches the mixing nozzle 50 that the fresh hydrocarbon feed fuel F does not exceed 400C. The configuration, thus, can further prevent carbon deposition and soot formation due to hydrocarbon cracking which occurs at temperatures above 400C.
According to one aspect of the invention, the reforming charnber 56 generally 30 comprises a walled vessel cont~inin~ a reforming catalyst material 58 therein, the reforming catalyst material having separate flow ch~nn~lc 59 extending along the flow - 21~278~
- 21 - 56,013 path of the reformable gas, directed toward the fuel cells, and the flow paths of one or both of the hot spent gas and the combusted exhaust gas directed in close proximity to the reformable gas flow paths. Heat energy passes through the body of the reforming chamber from one of the flow paths to the other. The flow path for at least 5 the reformable gas is lined with the reforming catalyst, and preferably the catalyst is included on the surfaces defining the reformable gas flow path.
A number of alternative specific structures for the reforming chamber 56 are possible. The reforming chamber 56 can have a circular, oval or rectangular cross section and can be more or less thick. Whereas the body of the reforming chamber 56 10 is traversed by the adjacent discrete passageways 59 def~ed in the reforming catalyst material 58, the separate flow paths 59 of the gases are defined in a manner that brings the gases into thermal ~l~nsrer relationship in a compact and effective manner.
Moreover, the flow paths 59 allow the reformable gas mixture 54 to traverse the reforming charnber 56 without substantial reduction in plessul'c across the catalyst.
In one embodiment as shown in FIGURE 2 and FIGURE 3, the reforming chamber 56 can contain a reforming catalyst material 58 comprising an elongated catalyst support material impregnated with reforming catalyst. The catalyst support is generally cylindrical and defines a plurality of flow passageways 59 for the reformable gas mixture 54, the flow passageways being disposed parallel to and at a radial di~t~n~e 20 from the central axis of the catalyst support. Preferably, the catalyst support material is made from non-rigid, porous, fibrous, substantially unsillLclcd, alumina that is impregnated with catalytic Ni and MgO. The plurality of radial-groove or slot passageways 59 can be integrally formed within the catalyst support material by known occlusion techniques such as, for example, by selectively COlll~lcSSillg the flow path 25 areas. The plurality of radial-groove or slot passageways 59 for the reformable gas Lule 54 are formed to extend radially inwardly from the outer cil~;ulllrelence to improve heat transfer and resistance to pressure drop across the catalyst material.
The groove or slot passageways 59 are closed on the outside by suitable reforming chamber cont~inm~nt walls 56, such as high lelllpel~ lc resistant Inconel 30 or the like, which can guide the hot spent fuel gas in the spent fuel gas recirculation channel 48 downwardly, as shown, or upwardly (not shown), to define either - 22 - 56,013 concurrent or countel~;ullcnt flow. The groove or slot passageways 59 can also be closed on the outside by a separate high temperature resistant metal walls such as Inconel. It is also possible that the separate passageways could be oriented in another manner or arranged for flows in other relative directions such as concurrent, 5 countelcùllent or cross flows in an electrochemical generator that was geneMlly configured dirÇelclllly. It is also possible that the catalyst material 58 comprise a catalyst support which also defines an axial passage closed by suitable inner reforming chamber cont~inm~nt walls or separate metal walls, the axial passageways being used for spent fuel gas and/or combusted exhaust gas to flow within. The catalyst material, 10 accordingly, includes an additional plurality of passageways 59 for the reformable gas mixture 54 disposed parallel to the axial passage and at a radial distance from the inner circulllrelel1ce as is shown in FIGURE 4.
FIGURE 4 and FIGURE 5 show an alternative embodiment in which the reforming catalyst material 58 comprises a catalyst support impregnated with catalyst 15 which is configured as a tubular and finned arrangement to define inner and outer flow channels 59 exten~1ing parallel to the axis of the generally tubular catalyst support material. Moreover, FIGURE 4 shows the reforming material 58 as stackable discs,each disc having the discrete flow paths 59 def~ed therein. The discs provide for easier assembly and tli.~semhly of the catalyst material in the reforming chamber.
20 The catalyst material is confined by inner and outer tubular walls, for example, the reforming ch~mher walls 56, of thermally conductive material, such as Inconel, thereby defining separate passageways for the reformable gas mixture 54. The surfaces at- which the le~ollllable gas mixture 54 contacts the reforming catalyst material 58 in this case is deflned by generally rectangular grooves or slots 59 along the direction of 25 ~follllable gas flow. Other shapes are also possible. Furthermore, the grooves can define irregular shapes, for exarnple defining a scalloped or rippled surface, for providing irlcreased surface area along the flow paths.
Referring again to the embodiment in FIGURE 1, the reforming chamber 56 is preferably arranged in an axially elongated tube for accepting the reforming catalyst 30 material 58 therein and to couple the reforrnable gas mixture fuel inlet 60 and reformed gas fuel outlet 62. At least this passage for the reformable gas mixture 54 contains a 21~2781 - 23 - 56,013 reforming catalyst material 58 including catalyst support and catalyst as generally shown in FIGURES 2 and 4. The reforming chamber containment walls 56, therefore,enclose around the outside of the reforming material 58 and can define part of the walls of the separate flow channels 59 (~, the outermost channels in FIGURE 2 and bothS the outermost and innermost channels in FIGURE 4.) For this purpose, the reforming catalyst material 58 includes a catalyst supportbody which is preferably made of a self-supporting material, preferably comprising a self-supporting, porous alumina material which is impregnated with catalytic Ni and possibly MgO, and optionally promoters. The reforming catalyst material 58 having 10 the configuration according to the invention can comprise conventional rigid, pressed or sintered alumina catalyst support implG~sl~tGd i.e., distributed throughout the bulk of the catalyst support material, with a reforming catalyst. However, a conventional rigid catalyst support is not preferred. According to the other aspect of the invention as explained more fully hereinafter, it is most preferable for the reforming catalyst 15 material 58 comprise a non-rigid, porous, fibrous alumin~ support i~llplG~llated at least on the reformable gas mixture cont~cting surfaces with catalytic material, wherein the catalyst support is flexible and substantially not sintered, and then molded into the required shape to define the separate reformable gas cont~r-ting surfaces or flow channels 59 along the length of the catalyst support. The reforming catalyst typically 20 comprises catalytic Pt and Ni, preferably Ni, and can also comprise metal salts and metal oxides selected from the group of Mg, Ca-Al, Sr-Al, Zr, Y, Ce, Ba and mixtures thereof, preferably Mg and Ca, even more preferably Mg. A more detailed description of the reforming catalyst composition and method of impregnating the catalyst support with catalyst can be found in U.S. Patent No. 4,898,792 (Singh et al.), which is hereby 25 incorporated by lGrGrGnce.
Thus, rather than using a packed bed of commercial catalyst pellets contained within a reforming chamber cont~inment walls, and thus subst~nti~lly occluding the flow path, the reforming catalyst material 58 configuration having discrete passageways 59 defined along the length of the catalyst support according to the invention includes 30 a catalyst support that integrally exposes the impregnated reforming catalyst along surfaces that contact the reformable fuel gas mixture 54 without substantial pressure 21427~1 - 24 - 56,013 drops, while also defining adjacent passageways 59 for applopliate transfer of heat energy. The result is good heat transfer, a low pressure drop, a very compact, easy to assemble and efficient arrangement for the catalyst material 58 and the reforming chamber 56. The heat transfer can be further improved by partly defining certain of 5 the passageways by reforming chamber cont~inment walls 56 made of high temperature resistant thermally conductive material (~, metal), such passageways being also partly defined by outer surfaces of the catalyst material 58 itself.
Thus, the low pressure drop and high heat flux flow channels 59 defining the lefo""able gas cont~ting surfaces directs a substantial portion of the reformable gas 10 mixture 54 flow to be adjacent the hot reforming chamber wall 56 where the preferably-irregular surface receives thermal energy from the reforming chamber partitioning wall and transfers heat energy to the refo"llable gas mixture by radiation, conduction and convection. Therefore, the flow c~nn~-ls 59 provide superior heat~ld,~,rel to the reformable gas mixture, while m~int~ining close contact between the 15 catalytic sites and the reformable gas stream. By using this reforming catalyst material configuration, a signifir~nt increase in heat transfer area per reformer volume can result. Therefore, this catalyst configuration is particularly adaptable to many compact geometries, which would not be practical with commercial catalyst pellets.
The flow ch~nn~ols 59 additionally allow for a substantially unobstructed flow 20 path of the reformable gas mixture 54 through the reforming chamber 56 and s~bst~nti~lly reduce pl`~S~,ul`e drop in the reforming chamber. This is particularly advantageous in a fuel cell generator apl)dldLus where ~Ulll~illg pressu~ available to drive the reformable gas lllL~ le 54 through a reforming catalyst material 58 is limi~d.
Moreover, the use of elongated pieces of reforming catalyst material configured with 25 integral flow channels 59 defined in the catalyst support along the corli,-~-..-- thereof can also provide significant improvement in the catalyst in~t~ tion and removal process over that required for loose catalyst pellets in a reforming chamber.
It will be appreciated that other particular configurations having such integrally formed separate flow paths are also possible. Additionally, the invention can be30 applied to other specific flow configurations for electrochemical generators having internal catalytic hydrocarbon reforming chambers, for example, as taught in U.S.
- 25 - 56,013 Patents 4,983,471 (Reichner et al.); 5,047,299 (Shockling); 5,082,751 (Reichner);
5,143,800 (George et al.); and, 5,169,730 (Reichner), which are hereby incorporated.
According to the other aspect of the invention, the reforming catalyst material 58 comprises a porous, non-rigid and, thus, flexible catalyst support material which 5 subst~nti~lly reduces mechanical or dimensional breakdown of the reforming catalyst material 58 that is believed to result from slow deposition or buildup of carbon on the reforming catalyst material upon prolonged reforming operations.
It is known that the long term operation of a hydrocarbon fueled electrochemicalgenerator, such as a high temperature, solid oxide electrolyte fuel cell generator 10 cont~ining an internal reforming chamber contAining commercial reforming catalyst pellets cause problems. Commercial rigid, porous, sintered alumina catalyst supported, nickel-based reforming catalyst pellets are prone to mechanical degradation, pulverization and dusting, due to slow deposition of carbon. Carbon deposition leads to a pressure buildup across the reformer bed and, consequently, degradation of the 15 generator's electrical output. Structural and chemical analysis of a disintegrated and pulverized catalyst in a electroch~omir~l generator has shown that the mechanical breakdown is due to carbon formation in the catalyst, especially filamentary carbon formation.
FIGURE 6 shows a conventional rigid sintered alllmin~ catalyst support material 20 impregnated with reforming catalyst having a surface morphology of carbon formed thereon after operation in a high le~ ,cldlulc, solid oxide fuel cell generator at 500C
in the presence of carbon forming gases of a CH4-H2O gas mixture having a steam to carbon ratio of 1:1 for about 65 hours. Moreover, the commercial rigid catalyst material experienced severe mech~nir~l disintegration and pulverization of the catalyst 25 support structure. Thus, changes in the catalyst support body material chemistry and carbon formation over time are detrimental to the catalyst support stability.
However, the porous, non-rigid, fibrous, substantially unsullelcd, reforming catalyst material 58 according to the invention is characterized by an alumina catalyst support that is not rigidly sintered or pressed to rigidity and, therefore, is not 30 c_aracterized by extensive rigid interparticle and interfiber bonding. Thus, the re~orming catalyst support does not contain rigid sintered contacts between granular or 214278~
- 26 - 56,013 fibrous supports. In the absence of these rigid contacts, the catalyst support is flexible and compressible and remains substantially resistant to dimensional and mechanical degradation, puiverization, dusting and fracturing during carbon formation and further during subsequent removal of carbon from the support by oxidation. The non-rigid5 alumina support is made from alumina fibers interwoven together that make it flexibly colllp~ssible and substantially resistant to internal stresses developed in the catalyst material due to carbon deposition. The density of the non-rigid, porous, substantially unsintered, fibrous, catalyst support is preferably between 1545 lb/ft3, typically 15 lb/ft3, 30 lb/ft3, or 45 lb/ft3. The non-rigid, porous, alumina support is preferably 10 treated or impregnated with catalytic Ni to reform the hydrocarbons and also MgO to improve H2O adsorption. The catalytic doping materials, e.g. Pt and Ni, preferably Ni, and modifiers, e g. metal salts and metal oxides selected from the group of Mg, Ca-Al, Sr-Al, Zr, Y, Ce, Ba and mixtures thereof, preferably Mg and Ca, even more preferably Mg, and the method of impregnation on the catalyst support are taught in U.S. Patent No. 4,898,792 (Singh et al.), which is hereby incorporated.
The flexible or compressible catalyst support material according to the invention remains flexible during reforming operations and, therefore, upon the slow deposition of carbon on the surfaces thereof, it is not subjected internal stresses that accompany conventional materials. It therefore remains substantially intact over prolongedoperations. The catalyst supports remains flexible by being made from fibers and not being substantially sintered.
The invention will be further clarifled by a consideration of the following example, which is intended to be purely exemplary of the use of the invention.
A reforming catalyst material according to the invention was prepared by hllplegndtillg a non-rigid, porous, substantially u~ lel~d~ alumina support material (fibrous alumina (Al2O3) based insulation material (ZAL-15)) with Ni and MgO by the method of impregnation disclosed in U.S. Patent No. 4,898,792 (Singh et al.). The reforming catalyst material was then positioned in a reforming chamber of a high~lllpeldture, solid oxide electrolyte generator apparatus, such as shown in FIGURE 1, 21427~1 - 27 - 56,013 in the presence of a CH4-H2O gas mixture (steam to carbon ratio of 1:1) at 500C for about 65 hours. A commercial prior art rigid, sintered alumina catalyst support impregnated with Ni and MgO in the form of pellets was also prepared and tested as described above.
S FIGURE 7 shows the non-rigid, substantially unsintered, fibrous, alumina reforming catalyst support impregnated with Ni and MgO according to the invention (top) in comparison to a commercial prior art rigid, sintered, alumina reformingcatalyst support pellet (bottom) after prolonged operation in the high temperature, solid oxide electrolyte fuel cell generator. The conventional catalyst support impregnated with catalyst shows severe mech~nic~l disintegration, pulverization, fracturing and dusting of the catalyst support due to carbon deposition, whereas the non-rigid reforming catalyst support treated with catalyst according to the invention remains structurally and dimensionally stable without any substantial dusting or pulverization.
The reforming catalyst material according to this aspect of the invention can beconfigured as described above according to the other aspect of the invention. The reforming catalyst material can also be positioned in a reforming chamber as a contimn~m or in conjunction with a catalyst pellet bed.
The invention having been disclosed in connection with the foregoing variations and examples, additional variations will now be apparent to persons skilled in the art.
The invention is not intended to be limited to the variations specifically mentioned, and accordingly lel~lcllce should be made to the appended claims rather than the foregoing disc~ssion of plcfcll~d examples, to assess the scope and spirit of the invention in which exclusive rights are cl~im~d
However, this configuration is not space or volume efficient. Moreover, it results in 5 a relatively high pressure drop of the reformer gas stream through the catalyst bed.
Some proposed hydrocarbon reformer applications are extremely limited in available space allocation and also in pumping pressure available to drive the reformer gas through the catalyst bed. An example is an internal reformer for a high temperature, solid oxide fuel cell recirculation generator incorporating an ejector or nozzle as the 10 gas stream motive element. There is a need for a more optimal configuration of the reforming chamber and the reforming catalyst material contained therein including the catalyst support structure and catalyst deposited thereon, to improve heat transfer rates and resistance to pressure drops.
It would be advantageous for catalytic hydrocarbon reformers, especially in an 15 electrochemical fuel cell generator appaldLus, to contain a reforming catalyst material having a catalyst support structure impregnated with catalyst that is not prone to mechanical or dimensional breakdown due to carbon formation, improves gas streampressure drop through the catalyst bed, and enables a high heat flux to pass from the catalyst cont~inment wall to the lcro"l,able gas stream. According to one aspect of 20 the present invention, a catalyst material is provided including a porous, non-rigid catalyst support material impregnated with a reforming catalyst. The non-rigid, catalyst support is colll~lcssible and improves the stability of the catalyst support against pulverization. Moreover, even in the event of generation operation wherecarbon formation may occasionally become possible, the non-rigid catalyst support of 25 the invention provides structural stability to the catalyst material without pulverization of the catalyst support or the catalyst. According to another aspect of the present invention, a catalyst material is provided including a catalyst support configuration elongated in the direction of reformable gas flow having discrete flow paths or passageways along the catalyst support body to define a reformable gas mixture flow 30 channel or channels therein which provide passageways for the reformable gas mixture at lower plCS~ulc drops and heat transfer rates. The catalyst support configuration, - ~ 214278 1 - 9 - 56,013 therefore, defines discrete passageways along its length for substantial portions of the reformable gas mixture, improving heat transfer properties and reducing the pressure drop and purnping requirements across the catalyst bed.
21~2781 - 10- 56,013 Summary of the Invention It is an object of the invention to provide an electrochemical generator apparatus cont~ining an internal catalytic hydrocarbon reformer including a reforming catalyst material comprising an improved reforming catalyst support material.
5It is another object of the invention to provide a reforming catalyst support material that is non-rigid, flexible and compressible.
It is another object of the invention to provide a reforming catalyst support material having dimensional stability that is not prone to mechanical degradation and pulverization of the catalyst support and catalyst thereon and its support structure 10during prolonged operations.
It is a further object of the invention to provide an electrochf~mi~l generator apparatus cont~ining an internal catalytic hydrocarbon reformer including a reforming catalyst material comprising an illlprov~d reforming catalyst support configuration.
It is yet another object of the invention to provide a reforming catalyst support 15configuration defining flow channels or passageways therein for passage of a lerollllable gas mixture stream that improves heat transfer characteristics and further reduces refollllable gas mixture stream ~,les~ule drops across the catalyst support.
It is a further object of the invention to provide a catalytic hydrocarbon reformer having a reforming catalyst support configuration that is compact.
20It is an advantage of the invention to provide a reforming catalyst material that is not degraded by carbon formation during prolonged use.
It is another advantage of the invention to provide a reforming catalyst material having a low gas stream ~lcs~ule drop through the lerollllillg catalyst support material.
It is another advantage of the invention to provide a lerolllPillg catalyst material 25having a high heat flux between the reforming catalyst support material cont~inment wall and the refo~nable gas mixture stream.
One aspect of the invention resides in a reforming catalyst material comprising a catalyst support illlpregllated with catalyst characterized by the catalyst support being made of a non-rigid, porous, fibrous catalyst support material, wherein the fibers are 30compressible and subst~nti~lly unsinlel~d. The catalyst support is preferably made from ~ min~ and preferably impregnated with catalytic Ni and MgO. The catalyst _ 56,013 support is preferably elongated in the direction of reformable gas flow. The non-rigid and compressible nature of the catalyst support improves dimensional stability during carbon formation in reforming operations.
In another aspect of the invention resides in a reforming catalyst material S configuration characterized by a porous reforming catalyst support impregnated with catalyst, where the catalyst support is elongated in a direction of flow of a reformable hydrocarbon gas, and where a reformable gas conf~rting surface of the catalyst support defines at least one discrete passageway extending along the length of the catalyst support to form a reformable gas flow channel, the at least one discrete passageway being in heat co~ -nication with means for heating the reformable hydrocarbon gas in the at least one discrete passageway. Preferably, the catalyst support is characterized by a plurality of discrete passageways extending along the length of the catalyst support forming a plurality of gas flow channels, where at least one of the gas flow channels carries the reformable hydrocarbon gas. The discrete passageways are preferably formed at least partly by integral slots extending inwardly into the catalyst support and elongated in the direction of gas flow, and there is preferably at least one col~ling wall made from a high telllpelature resistant, thermally conductive material disposed around the catalyst support, where the confining wall partly closes the integral slot. The catalyst support impregnated with catalyst configuration according to the invention configured to define discrete reformable hydrocarbon gas flow channelsimproves reformable hydrocarbon gas stream pres~ure drop through the catalyst bed of the reforming chamber, enables a high heat flux to exist from the catalyst support cont~inm~nt wall to the reformable gas stream disposed in the flow channels, andallows for compactn~oss of design.
Another aspect of the invention resides in an electrochemical generator appalalus, especially a high temperature, solid oxide electrolyte fuel cell generator, comprising; an elongated generator chamber cont~ining at least one cell bundle, the bundle cont~ining a plurality of parallel, elongated electrochemical cells, each cell having an exterior fuel electrode, an interior air electrode, and a solid oxide electrolyte thelcb~lween, a fresh gaseous feed fuel inlet to the generator chamber, a gaseous feed oxidant inlet to the generator chamber, at least one gaseous spent fuel exit from the - 12- 56,013 generator chamber, a combustion chamber, at least one gaseous combusted exhaust exit from the combustion chamber, and, a reforming chamber cont~ining a hydrocarbon reforming catalyst material comprising a catalyst support impregnated with a reforming catalyst, where a spent fuel exit channel passes from the generator chamber to combine 5 with a fresh hydrocarbon feed fuel inlet at a mixing chamber, and a reformablehydrocarbon gas mixture passes from the mixing chamber to the reforming chamber,wherein the reformable hydrocarbon gas mixture is substantially reformed and passes from the reforming chamber into the generator chamber, and, further wherein the a reformable gas contacting surface of the reforming catalyst support impregnated with 10 catalyst comprises at least one discrete passageway formed at least partly integrally in the reforming catalyst support and ext~n-ling along the length of the reforming catalyst support in the direction of reformable hydrocarbon gas flow forming a reformable gas flow channel, the at least one discrete passageway being in heat comm--ni~-~tion with means for heating the reformable hydrocarbon gas in said at least one discrete 15 passageway. Preferably, the reformable gas cont~cting surface of the catalyst support comprises a plurality of discrete passageways disposed adjacent one another in the catalyst support. Preferably, the means for heating said reformable hydrocarbon gas comprises said spent gas exit or combusted exhaust gas exit which is directed in heat co""",l.lir~tion with a wall of the reforming chamber, wherein the wall of the 20 reforming chamber is disposed around the catalyst support, partly closing the at least one discrete passageway. Further, the reforming catalyst material is preferably made of a non-rigid, porous, fibrous catalyst support material, wherein the fibers are c~ essible and subst~nti~lly ul~illL~red, and ill~lcgllatcd with catalytic Ni and MgO.
- 13- 56,013 Brief Description of the Drawin~s There are shown in the drawings certain exemplary embodiments of the invention as presently preferred. It should be understood that the invention is not limited to the embodiments disclosed as examples, and is capable of variation within the scope of the appended claims. In the drawings, FIGURE 1 is a section view along an axial plane, through one embodiment of a high temperature, solid oxide electrolyte electrochemical generator including an internal reforming chamber 56 cont~ining a reforming catalyst material comprising a reforming catalyst support configured according to the invention impregnated with catalyst, shown partly cut away along a direction of axial elongation.
FIGURE 2 is a lateral section view of a monolithic reforming catalyst material c~lllplising a catalyst support arrangement according to an embodiment, showing separate adjacent gas passageways integrally defined within the catalyst support for reducing pressure drop across the catalyst material and for transferring thermal energy from the hot gases to the reformable gases, at least the latter being heated in the presence of a reforming catalyst doped on the catalyst support.
FIGURE 3 is a top view of the catalyst material of FIGURE 2.
FIGURE 4 is a lateral section view of a finned reforming catalyst material including a catalyst support a~ gelllent according to the invention, showing a plurality of comra~t, stackable discs, each disc having sepaldl~ adjacent passageways integrally defined with each catalyst support disc, for reducing pressure drop across the catalyst material and for lldl~llhlg thermal energy from the hot gases to the reformable gases, at least the latter being heated in the presence of a lefoll~ g catalyst doped on the catalyst support.
FIGURE 5 is a top view of the catalyst material of FIGURE 4.
FIGURE 6 is an electron micrograph of a conventional rigid, porous, sintered reforming catalyst support made of alumina, and impl~ dted with Ni catalyst and MgO showing a surface morphology of carbon formed on the surface thereof after operation in a high tem~l~ture, solid oxide electrolyte electrochemical generator similar to the one shown in Figure 1 at 500C in a steam:carbon ratio of 1:1.
- 14- 56,013 FIGURE 7 is an electron micrograph of a catalyst material comprising a non-rigid, porous, fibrous, substantially unsintered, reforming catalyst support material, made from alumina, impregnated with reforming catalyst, Ni and MgO, according tothe invention compared to a prior art rigid, porous, sintered reforming catalyst support, 5 made from alumina, impregnated with reforming catalyst, Ni and~ MgO, after prolonged operation in a high te~eldlul~, solid oxide electrolyte electrochemical generator similar to the one shown in Figure 1 at 500C in a steam:carbon ratio at 1:1.
2142~8 1 - 15- 56,013 Detailed Description of the Preferred Embodiments The term "fuel electrode" as used herein means that electrode in contact with hydrocarbon fuel, the term "air electrode" as used herein means that electrode in contact with air or oxygen. The terms "spent" fuel or "spent" oxidant as used herein 5 refer to partially reacted, low BTU fuel, or partially reacted, depleted oxidant, e.~., cont~ining about 5 to 15% oxygen, respectively. The term "spent" does not include the mixture of the spent fuel combusted with spent oxidant, which mixture is described herein as "combusted exhaust" gas.
Referring to FIGURE 1, an electrochemical apparatus or generator 10 is shown 10 cont~ining cell bundles 12 and 14, each bundle having a plurality of parallel elongated electrochemical fuel cells 16, such as solid oxide electrolyte fuel cells. The fuel cells are located in a generator chamber 22, and can be arranged with the cells or bundles arranged in a rectangular or circular configuration, etc.
Each fuel cell 16 has an exterior fuel electrode 18 covering its elongated 15 surface, shown as a stippled section for the sake of clarity, an interior air electrode, and a solid oxide electrolyte between the electrodes. The air electrode and electrolyte are not shown specifically in FIGURE 1, and can be arranged in a manner that is known in the art.
The air electrode can be a doped ceramic of the perovskite family, for example, 20 doped LaMnO3. The electrolyte can by yttria-stabilized zirconia. The fuel electrode can be a zirconia-nickel cermet material. A calcia stabilized zirconia support for the air electrode can optionally be used. For a detailed description of the materials and construction of an exemplary fuel cell, reference can be made to U.S. Patent No.4,490,444 (Isenberg) and U.S. Patent No. 4,751,152 (Zymboly), which are hereby 25 incorporated by reference.
The electroch~mir~l generator al)pdldlus is intentle~ to operate with an interior temperature in the range of about 600C to about 1200C. An outer housing 20 generally surrounds the electrochemical generator apparatus. The housing is typically comprised of a high leml)eldlule resistant metal such as Inconel or the like. An inner 30 housing (not shown) can ~ulloul1d a plurality of chambers including the generator chamber 22 and a combustion chamber 24. The inner housing, if any, can also 21~2~81 - 16- 56,013 comprise a high temperature resistant metal such as Inconel. Thermal insulation 26, such as low density alumina, preferably is disposed within the outer housing 20.Penclldlulg the housing 20 and insulation 26 are a fresh hydrocarbon feed fuel inlet 28, where the fresh hydrocarbon feed fuel is shown as F, and an oxidant feed 5 inlet 30, where the oxidant such as air is shown as O. Ports can also be provided for electrical leads and the like (not shown).
The generator chamber 22 extends between a wall 32 and a porous barrier 34.
The porous barrier 34 is designed to allow spent fuel gas to exit, as in~ atPd by arrows 36, from the generator chamber 22 to the combustion chamber 24. The 10 generator chamber operates at a lJlCS~Ulc slightly above atmospheric, and thecombustion chamber 24, operates at a slightly lower pres~u,c than the generator chamber. The spent gas 36 combines with spent oxidant, as indicated by arrows 46, forming a hot combusted exhaust gas, as shown as E, which passes through combusted exhaust channel 38.
High tellllJe~dLulc, elongated, solid oxide electrolyte fuel cells 16 extend between the combustion chamber 24 and wall 32 and are disposed in generator chamber 22. The fuel cells 16 have open ends 40 at the combustion chamber 24, and closedends near wall 32, leading to the generator chamber 22. Each individual cell gencldles approximately one volt at nominal loading, and a plurality of cells are electrically interconntocted through conductive felts 42, typically nickel fiber metal. The cells can be connPctPd in a series-parallel array, as described in U.S. Patent 4,395,468 (Isenberg), which is hereby incorporated by lcfclc~lce, to obtain a desired relationship of output voltage to current capacity.
By way of example, during operation of the electro~hl~rnir~l ge~ alor apparatus 10, a gaseous oxidant O, such as air, is fed through oxidant feed inlet 30, and enters oxidant feed conduits 44, for example at a tclllpeldlule of approximately 500C to 700C, and above atmospheric p,cs~uic. The oxidant optionally can be heated prior to entering the housing by conventional means, such as a heat exchanger coupled with a blower. The oxidant in conduits 44 is then passed through the combustion chamber 24, where it is further heated to a telllpcldlulc of approximately 800C to 900C by the combusted e~h~llst gas E. The oxidant then flows through the length of the oxidant ` - 2142781 - 17- 56,013 circuit, through the conduits 44 which extend down the interior length of the fuel cells 16, being further heated to approximately 1000C, by virtue of absorbing most of the heat generated during the electrochemical reaction. A smaller fraction of the heat is absorbed by the fuel.
The oxidant is discharged into the closed end bottom of the fuel cells 16. The oxidant within the fuel cells reverses direction, and electrochemically reacts at the inner air electrode along the inside active length of the fuel cells, being depleted somewhat in oxygen content as it approaches the opposite open end 40 of the fuel cells 16.
The oxidant is reduced at the air electrode-electrolyte interface, supplying oxygen ions which migrate through the electrolyte to the fuel electrode-electrolyte interface where they are oxidized in the presence of reformed hydrocarbon fuel to produce electrons which flow through an external load circuit to the air electrode, thus gelle,aling a flow of electrical current. The electrochemical reactions at the air and fuel electrodes where hydrogen is used as a fuel, for example, are given by the following equations:
2 + 4e~ . 2o2- (air electrode) 202- + 2H2 2H2O + 4e~ (fuel electrode).
A more complete description of the operation of this type of electroch~ al cell can be found in U.S. Patent No. 3,400,054 (Ruka), which is hereby incorporated.
The depleted or spent oxidant is then discharged into the combustion chamber 24 through the open fuel cell ends 40, and is shown as spent oxidant exit streams 46.
The spent oxidant 46 combusts with depleted or spent fuel, part of which passes through porous barrier 34 as shown by arrow 36, to form combusted exhaust gas, which exits the app~lus, for example, through one or more combusted exhaust channels 38, f~ally exiting as the exhaust gas shown as E. The combusted exhaust gas E can be directed to pass in heat l,~rer co~ ni~-~tion with the wall of a reformer prior to exiting the apparatus. The combusted exhaust channels 38 can be made of a high lel~ .alu,e ,~si~la,ll metal, such as Inconel.
214278l - 18- 56,013 In the invention, a gaseous hydrocarbon feed fuel F that has not yet been reformed, such as a gaseous hydrocarbon, including hydrocarbons such as methane,ethane, propane and the like, vaporized petroleum fractions such as naphtha, alcohols such as ethyl alcohol and the like, and/or natural gas, can be fed to the electrochemical S generator apparatus through fresh feed fuel inlet channel 28. For example, a mixture of 85% methane, 10% ethane with a balance of propane, butane and nitrogen, can be fed into the electrochemical generator apparatus through fresh hydrocarbon feed fuel inlet channel 28 and reformed in a reforming chamber 56 into combustible compounds less likely to produce carbon formations and soot on a catalyst material 58 within the 10 reforming chamber 56. The term "catalyst material" as used herein refers to areforming catalyst support material having a reforming catalyst treated, impregnated or doped thereon, and optionally including other promoters or the like.
In the embodiment shown in FIGURE 1, a major portion of the hot, gaseous spent fuel formed along the length of the fuel cells 16 passes to at least one spent fuel 15 recirculation channel 48. Spent fuel recirculation channel 48 likewise can be made of a high temperature resistant metal such as Inconel. Another portion of the hot spent fuel passes into a combustion chamber 24, as previously shown by arrow 36, to combust with spent oxidant, as previously shown by arrow 46, and to preheat the fresh oxidant feed O. The spent fuel recirculation channel 48 cont~ining spent fuel passes 20 from the generator chamber 22 to feed into and combine with the fresh hydrocarbon feed fuel cont~ining feed fuel F at a mixing apparatus 50.
The mixing apparatus S0 can be any known type in the art, for example, an ejector, jet pump, nozzle, aspirator, mixer-nozzle/mixer-diffuser or the like. This allows recirculation of a portion of the spent fuel fed into spent fuel recirculation 25 channel 48 to mix with the fresh hydrocarbon feed fuel F fed through inlet 28 at the mixing apparatus S0 to produce a reformable gas fuel mixture, as shown by arrows 54.
In addition, the mixer optionally can be designed such that the dynamic energy of the fuel mixture at the entrance to the mixer S0, such as a nozzle, is effectively converted to an elevated pressure at an ell~ldnce to a reforming chamber 56 by a diffuser 52, the 30 cross-sectional area of which gets larger as it proceeds from its entrance near the nozzle, to the reforming chamber 56.
- 214!27~1 - 19- 56,013 Prior to passing through the catalytic hydrocarbon reforming chamber 56, the reformable gas fuel mixture 54 generally contains at least H2O vapor (steam), and typically also H2, CO and CO2, all contributed by the spent fuel that enters the mixer apparatus 50 through the spent fuel recirculation channel 48. Preferably, the volume 5 ratio of spent f~el to fresh feed fuel is adjusted by controlling the velocity of the fresh feed fuel input in the mixing apparatus 50 so that approximately two volumes to five volumes of H2O (steam) and CO2 are added to each volume of fresh feed fuel. A
preferred O:C volume ratio is from about 1.2:1 to 3:1 for a natural gas fueled electroch~mi~l fuel cell gellel~tor. The presence of H20,g, and/or CO2 plus a 10 reforming catalyst material allows for the conversion of gaseous hydrocarbons to CO
and H2 and reduces the rate of carbon formation due to hydrocarbon cracking.
The reforming reactions for methane and ethane (natural gas) using water and carbon dioxide, for example, are given by the following equations:
CH4 + H2O CO + 3H2 (1) CH4 + CO2 2CO + 2H2 (2) and, C2H6 + 2H2O 2CO + SH2 (3) C2H6 + 2CO2 4CO + 3H2 (4) The reforming reaction is endothermic and best performed at a temperature of 20 about 900C.
In the embodiment shown in FIGURE 1, the hydrocarbon reformable gaseous fuel mixture 54 next passes from the exit of the mixing apparatus through a catalytic hydrocarbon reforming chamber 56 cont~ining a hydrocarbon reforming catalyst material 58 cartridge comprising a self-supporting catalyst support material that is 25 treated with a reforming catalyst and optionally also treated with promoters or the like.
The reformable gas llli~-tUl`e iS reformed into a relatively low carbonizing fuel, as shown by arrows 64, and exits the reforming chamber into the generator chamber 22 through generator chamber entry ports 66 parallel to the generator chamber 22.
The reforming chamber 56, as shown in FIGURE 1, can contain, for example, 30 a reforming catalyst material 58 having an elongated, cylindrical, catalyst support configuration that defines elongated flow rh~nn~ls or passageways 59 extending through - 2l~27~l - 20 - 56,013 catalyst material 58 positioned in the reforming chamber 56, elongated in the direction of the reformable gas flow path. The channels can be defined in part by annular openings between concentric tubular sections, axial slots, grooves or channels, and/or otherwise formed as explained more fully hereinafter. The reforming chamber 56 can 5 be made of a high temperature resistant metal such as Inconel and configured to accept the reforming catalyst material 58 correspondingly configured therein.
The spent fuel recirculation channel 48 is preferably arranged for th~ lly conductive contact with the means defining the flow channels 59 of the reformingchamber 56, to allow heat transfer between hot spent gas in the recirculation channel 48 and the reformable gases 54 passing through the reforming chamber 56. This arrangement llal~fel~ heat energy from the recirculated spent fuel to provide heat energy needed for the endothermic reforming reaction, which is best perforrned at approximately 900C. Additionally, according to the embodiment in FIGURE 1, the recirculated spent fuel continues in recirculation channel 48 down and around to the 15 mixing nozzle 50 and in contact with the outside of the mixer diffuser chamber 52 with a further transfer of heat energy to the reformable fuel gaseous mixture 54 as it approaches the reforming chamber 56.
The combusted exhaust gas channel 38 can also optionally be arranged for thermal ~ rel to the reforming chamber 56 to provide additional heat to the reformer 20 in a similar ~ . For example, the combusted exhaust gas channel 38 can be arranged to pass through an annular opening between collcellL,ic tubular sections of the r~folllling chamber.
Further, in the embodiment FIGURE 1, the telll~lalure of the spent fuel can be reduced from approximately 1000C at the ~llll~ue to the recirculation fuel channel 25 48 to a suffuiently low lem~l~lure as it approaches the mixing nozzle 50 that the fresh hydrocarbon feed fuel F does not exceed 400C. The configuration, thus, can further prevent carbon deposition and soot formation due to hydrocarbon cracking which occurs at temperatures above 400C.
According to one aspect of the invention, the reforming charnber 56 generally 30 comprises a walled vessel cont~inin~ a reforming catalyst material 58 therein, the reforming catalyst material having separate flow ch~nn~lc 59 extending along the flow - 21~278~
- 21 - 56,013 path of the reformable gas, directed toward the fuel cells, and the flow paths of one or both of the hot spent gas and the combusted exhaust gas directed in close proximity to the reformable gas flow paths. Heat energy passes through the body of the reforming chamber from one of the flow paths to the other. The flow path for at least 5 the reformable gas is lined with the reforming catalyst, and preferably the catalyst is included on the surfaces defining the reformable gas flow path.
A number of alternative specific structures for the reforming chamber 56 are possible. The reforming chamber 56 can have a circular, oval or rectangular cross section and can be more or less thick. Whereas the body of the reforming chamber 56 10 is traversed by the adjacent discrete passageways 59 def~ed in the reforming catalyst material 58, the separate flow paths 59 of the gases are defined in a manner that brings the gases into thermal ~l~nsrer relationship in a compact and effective manner.
Moreover, the flow paths 59 allow the reformable gas mixture 54 to traverse the reforming charnber 56 without substantial reduction in plessul'c across the catalyst.
In one embodiment as shown in FIGURE 2 and FIGURE 3, the reforming chamber 56 can contain a reforming catalyst material 58 comprising an elongated catalyst support material impregnated with reforming catalyst. The catalyst support is generally cylindrical and defines a plurality of flow passageways 59 for the reformable gas mixture 54, the flow passageways being disposed parallel to and at a radial di~t~n~e 20 from the central axis of the catalyst support. Preferably, the catalyst support material is made from non-rigid, porous, fibrous, substantially unsillLclcd, alumina that is impregnated with catalytic Ni and MgO. The plurality of radial-groove or slot passageways 59 can be integrally formed within the catalyst support material by known occlusion techniques such as, for example, by selectively COlll~lcSSillg the flow path 25 areas. The plurality of radial-groove or slot passageways 59 for the reformable gas Lule 54 are formed to extend radially inwardly from the outer cil~;ulllrelence to improve heat transfer and resistance to pressure drop across the catalyst material.
The groove or slot passageways 59 are closed on the outside by suitable reforming chamber cont~inm~nt walls 56, such as high lelllpel~ lc resistant Inconel 30 or the like, which can guide the hot spent fuel gas in the spent fuel gas recirculation channel 48 downwardly, as shown, or upwardly (not shown), to define either - 22 - 56,013 concurrent or countel~;ullcnt flow. The groove or slot passageways 59 can also be closed on the outside by a separate high temperature resistant metal walls such as Inconel. It is also possible that the separate passageways could be oriented in another manner or arranged for flows in other relative directions such as concurrent, 5 countelcùllent or cross flows in an electrochemical generator that was geneMlly configured dirÇelclllly. It is also possible that the catalyst material 58 comprise a catalyst support which also defines an axial passage closed by suitable inner reforming chamber cont~inm~nt walls or separate metal walls, the axial passageways being used for spent fuel gas and/or combusted exhaust gas to flow within. The catalyst material, 10 accordingly, includes an additional plurality of passageways 59 for the reformable gas mixture 54 disposed parallel to the axial passage and at a radial distance from the inner circulllrelel1ce as is shown in FIGURE 4.
FIGURE 4 and FIGURE 5 show an alternative embodiment in which the reforming catalyst material 58 comprises a catalyst support impregnated with catalyst 15 which is configured as a tubular and finned arrangement to define inner and outer flow channels 59 exten~1ing parallel to the axis of the generally tubular catalyst support material. Moreover, FIGURE 4 shows the reforming material 58 as stackable discs,each disc having the discrete flow paths 59 def~ed therein. The discs provide for easier assembly and tli.~semhly of the catalyst material in the reforming chamber.
20 The catalyst material is confined by inner and outer tubular walls, for example, the reforming ch~mher walls 56, of thermally conductive material, such as Inconel, thereby defining separate passageways for the reformable gas mixture 54. The surfaces at- which the le~ollllable gas mixture 54 contacts the reforming catalyst material 58 in this case is deflned by generally rectangular grooves or slots 59 along the direction of 25 ~follllable gas flow. Other shapes are also possible. Furthermore, the grooves can define irregular shapes, for exarnple defining a scalloped or rippled surface, for providing irlcreased surface area along the flow paths.
Referring again to the embodiment in FIGURE 1, the reforming chamber 56 is preferably arranged in an axially elongated tube for accepting the reforming catalyst 30 material 58 therein and to couple the reforrnable gas mixture fuel inlet 60 and reformed gas fuel outlet 62. At least this passage for the reformable gas mixture 54 contains a 21~2781 - 23 - 56,013 reforming catalyst material 58 including catalyst support and catalyst as generally shown in FIGURES 2 and 4. The reforming chamber containment walls 56, therefore,enclose around the outside of the reforming material 58 and can define part of the walls of the separate flow channels 59 (~, the outermost channels in FIGURE 2 and bothS the outermost and innermost channels in FIGURE 4.) For this purpose, the reforming catalyst material 58 includes a catalyst supportbody which is preferably made of a self-supporting material, preferably comprising a self-supporting, porous alumina material which is impregnated with catalytic Ni and possibly MgO, and optionally promoters. The reforming catalyst material 58 having 10 the configuration according to the invention can comprise conventional rigid, pressed or sintered alumina catalyst support implG~sl~tGd i.e., distributed throughout the bulk of the catalyst support material, with a reforming catalyst. However, a conventional rigid catalyst support is not preferred. According to the other aspect of the invention as explained more fully hereinafter, it is most preferable for the reforming catalyst 15 material 58 comprise a non-rigid, porous, fibrous alumin~ support i~llplG~llated at least on the reformable gas mixture cont~cting surfaces with catalytic material, wherein the catalyst support is flexible and substantially not sintered, and then molded into the required shape to define the separate reformable gas cont~r-ting surfaces or flow channels 59 along the length of the catalyst support. The reforming catalyst typically 20 comprises catalytic Pt and Ni, preferably Ni, and can also comprise metal salts and metal oxides selected from the group of Mg, Ca-Al, Sr-Al, Zr, Y, Ce, Ba and mixtures thereof, preferably Mg and Ca, even more preferably Mg. A more detailed description of the reforming catalyst composition and method of impregnating the catalyst support with catalyst can be found in U.S. Patent No. 4,898,792 (Singh et al.), which is hereby 25 incorporated by lGrGrGnce.
Thus, rather than using a packed bed of commercial catalyst pellets contained within a reforming chamber cont~inment walls, and thus subst~nti~lly occluding the flow path, the reforming catalyst material 58 configuration having discrete passageways 59 defined along the length of the catalyst support according to the invention includes 30 a catalyst support that integrally exposes the impregnated reforming catalyst along surfaces that contact the reformable fuel gas mixture 54 without substantial pressure 21427~1 - 24 - 56,013 drops, while also defining adjacent passageways 59 for applopliate transfer of heat energy. The result is good heat transfer, a low pressure drop, a very compact, easy to assemble and efficient arrangement for the catalyst material 58 and the reforming chamber 56. The heat transfer can be further improved by partly defining certain of 5 the passageways by reforming chamber cont~inment walls 56 made of high temperature resistant thermally conductive material (~, metal), such passageways being also partly defined by outer surfaces of the catalyst material 58 itself.
Thus, the low pressure drop and high heat flux flow channels 59 defining the lefo""able gas cont~ting surfaces directs a substantial portion of the reformable gas 10 mixture 54 flow to be adjacent the hot reforming chamber wall 56 where the preferably-irregular surface receives thermal energy from the reforming chamber partitioning wall and transfers heat energy to the refo"llable gas mixture by radiation, conduction and convection. Therefore, the flow c~nn~-ls 59 provide superior heat~ld,~,rel to the reformable gas mixture, while m~int~ining close contact between the 15 catalytic sites and the reformable gas stream. By using this reforming catalyst material configuration, a signifir~nt increase in heat transfer area per reformer volume can result. Therefore, this catalyst configuration is particularly adaptable to many compact geometries, which would not be practical with commercial catalyst pellets.
The flow ch~nn~ols 59 additionally allow for a substantially unobstructed flow 20 path of the reformable gas mixture 54 through the reforming chamber 56 and s~bst~nti~lly reduce pl`~S~,ul`e drop in the reforming chamber. This is particularly advantageous in a fuel cell generator apl)dldLus where ~Ulll~illg pressu~ available to drive the reformable gas lllL~ le 54 through a reforming catalyst material 58 is limi~d.
Moreover, the use of elongated pieces of reforming catalyst material configured with 25 integral flow channels 59 defined in the catalyst support along the corli,-~-..-- thereof can also provide significant improvement in the catalyst in~t~ tion and removal process over that required for loose catalyst pellets in a reforming chamber.
It will be appreciated that other particular configurations having such integrally formed separate flow paths are also possible. Additionally, the invention can be30 applied to other specific flow configurations for electrochemical generators having internal catalytic hydrocarbon reforming chambers, for example, as taught in U.S.
- 25 - 56,013 Patents 4,983,471 (Reichner et al.); 5,047,299 (Shockling); 5,082,751 (Reichner);
5,143,800 (George et al.); and, 5,169,730 (Reichner), which are hereby incorporated.
According to the other aspect of the invention, the reforming catalyst material 58 comprises a porous, non-rigid and, thus, flexible catalyst support material which 5 subst~nti~lly reduces mechanical or dimensional breakdown of the reforming catalyst material 58 that is believed to result from slow deposition or buildup of carbon on the reforming catalyst material upon prolonged reforming operations.
It is known that the long term operation of a hydrocarbon fueled electrochemicalgenerator, such as a high temperature, solid oxide electrolyte fuel cell generator 10 cont~ining an internal reforming chamber contAining commercial reforming catalyst pellets cause problems. Commercial rigid, porous, sintered alumina catalyst supported, nickel-based reforming catalyst pellets are prone to mechanical degradation, pulverization and dusting, due to slow deposition of carbon. Carbon deposition leads to a pressure buildup across the reformer bed and, consequently, degradation of the 15 generator's electrical output. Structural and chemical analysis of a disintegrated and pulverized catalyst in a electroch~omir~l generator has shown that the mechanical breakdown is due to carbon formation in the catalyst, especially filamentary carbon formation.
FIGURE 6 shows a conventional rigid sintered alllmin~ catalyst support material 20 impregnated with reforming catalyst having a surface morphology of carbon formed thereon after operation in a high le~ ,cldlulc, solid oxide fuel cell generator at 500C
in the presence of carbon forming gases of a CH4-H2O gas mixture having a steam to carbon ratio of 1:1 for about 65 hours. Moreover, the commercial rigid catalyst material experienced severe mech~nir~l disintegration and pulverization of the catalyst 25 support structure. Thus, changes in the catalyst support body material chemistry and carbon formation over time are detrimental to the catalyst support stability.
However, the porous, non-rigid, fibrous, substantially unsullelcd, reforming catalyst material 58 according to the invention is characterized by an alumina catalyst support that is not rigidly sintered or pressed to rigidity and, therefore, is not 30 c_aracterized by extensive rigid interparticle and interfiber bonding. Thus, the re~orming catalyst support does not contain rigid sintered contacts between granular or 214278~
- 26 - 56,013 fibrous supports. In the absence of these rigid contacts, the catalyst support is flexible and compressible and remains substantially resistant to dimensional and mechanical degradation, puiverization, dusting and fracturing during carbon formation and further during subsequent removal of carbon from the support by oxidation. The non-rigid5 alumina support is made from alumina fibers interwoven together that make it flexibly colllp~ssible and substantially resistant to internal stresses developed in the catalyst material due to carbon deposition. The density of the non-rigid, porous, substantially unsintered, fibrous, catalyst support is preferably between 1545 lb/ft3, typically 15 lb/ft3, 30 lb/ft3, or 45 lb/ft3. The non-rigid, porous, alumina support is preferably 10 treated or impregnated with catalytic Ni to reform the hydrocarbons and also MgO to improve H2O adsorption. The catalytic doping materials, e.g. Pt and Ni, preferably Ni, and modifiers, e g. metal salts and metal oxides selected from the group of Mg, Ca-Al, Sr-Al, Zr, Y, Ce, Ba and mixtures thereof, preferably Mg and Ca, even more preferably Mg, and the method of impregnation on the catalyst support are taught in U.S. Patent No. 4,898,792 (Singh et al.), which is hereby incorporated.
The flexible or compressible catalyst support material according to the invention remains flexible during reforming operations and, therefore, upon the slow deposition of carbon on the surfaces thereof, it is not subjected internal stresses that accompany conventional materials. It therefore remains substantially intact over prolongedoperations. The catalyst supports remains flexible by being made from fibers and not being substantially sintered.
The invention will be further clarifled by a consideration of the following example, which is intended to be purely exemplary of the use of the invention.
A reforming catalyst material according to the invention was prepared by hllplegndtillg a non-rigid, porous, substantially u~ lel~d~ alumina support material (fibrous alumina (Al2O3) based insulation material (ZAL-15)) with Ni and MgO by the method of impregnation disclosed in U.S. Patent No. 4,898,792 (Singh et al.). The reforming catalyst material was then positioned in a reforming chamber of a high~lllpeldture, solid oxide electrolyte generator apparatus, such as shown in FIGURE 1, 21427~1 - 27 - 56,013 in the presence of a CH4-H2O gas mixture (steam to carbon ratio of 1:1) at 500C for about 65 hours. A commercial prior art rigid, sintered alumina catalyst support impregnated with Ni and MgO in the form of pellets was also prepared and tested as described above.
S FIGURE 7 shows the non-rigid, substantially unsintered, fibrous, alumina reforming catalyst support impregnated with Ni and MgO according to the invention (top) in comparison to a commercial prior art rigid, sintered, alumina reformingcatalyst support pellet (bottom) after prolonged operation in the high temperature, solid oxide electrolyte fuel cell generator. The conventional catalyst support impregnated with catalyst shows severe mech~nic~l disintegration, pulverization, fracturing and dusting of the catalyst support due to carbon deposition, whereas the non-rigid reforming catalyst support treated with catalyst according to the invention remains structurally and dimensionally stable without any substantial dusting or pulverization.
The reforming catalyst material according to this aspect of the invention can beconfigured as described above according to the other aspect of the invention. The reforming catalyst material can also be positioned in a reforming chamber as a contimn~m or in conjunction with a catalyst pellet bed.
The invention having been disclosed in connection with the foregoing variations and examples, additional variations will now be apparent to persons skilled in the art.
The invention is not intended to be limited to the variations specifically mentioned, and accordingly lel~lcllce should be made to the appended claims rather than the foregoing disc~ssion of plcfcll~d examples, to assess the scope and spirit of the invention in which exclusive rights are cl~im~d
Claims (26)
1. A hydrocarbon reforming catalyst material configuration, comprising a porous reforming catalyst support impregnated with catalyst, said catalyst support elongated in a direction of flow of a reformable hydrocarbon gas, wherein a reformable gas contacting surface of the catalyst support defines at least one discrete passageway extending along the length of the catalyst support forming a reformable gas flowchannel, said at least one discrete passageway is in heat communication with means for heating the reformable hydrocarbon gas in said at least one discrete passageway.
2. The hydrocarbon reforming catalyst material configuration of claim 1, wherein the reformable hydrocarbon gas contacting surface comprises a plurality of discrete passageways extending along the length of the catalyst support forming a plurality of gas flow channels, at least one of the gas flow channels carrying reformable hydrocarbon gas.
3. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the gas flow channels are formed at least partly by integral slots extending inwardly into the catalyst support and elongated in the direction of gas flow.
4. The hydrocarbon reforming catalyst material configuration of claim 3, further comprising at least one confining wall disposed around the catalyst support, the confining wall partly closing the integral slot.
5. The hydrocarbon reforming catalyst material configuration of claim 4, wherein the confining wall is made of a high temperature resistant, thermally conductive metal or alloy.
6. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the catalyst support is generally cylindrical and elongated in the direction of gas flow.
7. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the catalyst support is generally rectangular and elongated in the direction of gas flow.
8. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the catalyst support comprises a plurality of discs, stackable one upon each other.
9. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the catalyst support has at least one central passageway and at least one integral slot extending inwardly into the catalyst support body, the central passageway and slot being elongated in the direction of gas flow.
10. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the reforming catalyst material comprises a porous, alumina catalyst support impregnated with a reforming catalyst selected from the group of metals consisting of Ni and Pt.
11. The hydrocarbon reforming catalyst material configuration of claim 10, wherein the reforming catalyst further comprises metals or metal oxides selected from the group consisting of Mg, Ca-Al, Sr-Al, Ce and Ba.
12. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the reforming catalyst impregnated on the catalyst support comprises Ni and MgO.
13. The hydrocarbon reforming catalyst material configuration of claim 2, wherein the reforming catalyst material support comprises a non-rigid, porous, fibrous alumina catalyst support, wherein the fibers are compressible and substantially unsintered and are impregnated with Ni and MgO.
14. A hydrocarbon reforming catalyst material, comprising a non-rigid, porous, fibrous catalyst support impregnated with catalyst, wherein the fibers are compressible and substantially unsintered.
15. The hydrocarbon reforming catalyst material according of claim 14, wherein the catalyst support comprises alumina.
16. The hydrocarbon reforming catalyst material of claim 14, wherein the catalyst support is impregnated with catalyst selected from the group of metals consisting of Ni and Pt, and selected from the group of metals or metal oxides from the group consisting of Mg, Ca-Al, Sr-Al, Ce and Ba.
17. The hydrocarbon reforming catalyst material of claim 14, wherein the catalyst support is cylindrical and elongated in the direction of gas flow.
18. The hydrocarbon reforming catalyst material of claim 14, wherein the catalyst support is rectangular and elongated in the direction of gas flow.
19. The hydrocarbon reforming catalyst material of claim 14, wherein the catalyst support is in pellet form.
20. An electrochemical generator apparatus comprising:
an elongated generator chamber containing at least one cell bundle, the bundle containing a plurality of parallel, elongated electrochemical cells, each cell having an exterior fuel electrode, an interior air electrode, and a solid oxide electrolyte therebetween;
a fresh gaseous feed fuel inlet to the generator chamber;
a gaseous feed oxidant inlet to the generator chamber;
at least one gaseous spent fuel exit from the generator chamber;
a combustion chamber;
at least one gaseous combusted exhaust exit from the combustion chamber; and, a reforming chamber containing a hydrocarbon reforming catalyst material comprising a catalyst support impregnated with a reforming catalyst, wherein a spent fuel exit channel passes from the generator chamber to combine with a fresh hydrocarbon feed fuel inlet at a mixing chamber and a reformable hydrocarbon gas mixture passes from the mixing chamber to the reforming chamber wherein the reformable hydrocarbon gas mixture is substantially reformed and passes from the reforming chamber into the generator chamber, and, wherein the a reformable gas contacting surface of the reforming catalyst support comprises at least one discrete passageway formed at least partly integrally in the reforming catalyst support and extending along the length of the reforming catalyst support in the direction of reformable hydrocarbon gas flow forming a reformable gas flow channel, said at least one discrete passageway being in heat communication with means for heating the reformable hydrocarbon gas in said at least one discrete passageway.
an elongated generator chamber containing at least one cell bundle, the bundle containing a plurality of parallel, elongated electrochemical cells, each cell having an exterior fuel electrode, an interior air electrode, and a solid oxide electrolyte therebetween;
a fresh gaseous feed fuel inlet to the generator chamber;
a gaseous feed oxidant inlet to the generator chamber;
at least one gaseous spent fuel exit from the generator chamber;
a combustion chamber;
at least one gaseous combusted exhaust exit from the combustion chamber; and, a reforming chamber containing a hydrocarbon reforming catalyst material comprising a catalyst support impregnated with a reforming catalyst, wherein a spent fuel exit channel passes from the generator chamber to combine with a fresh hydrocarbon feed fuel inlet at a mixing chamber and a reformable hydrocarbon gas mixture passes from the mixing chamber to the reforming chamber wherein the reformable hydrocarbon gas mixture is substantially reformed and passes from the reforming chamber into the generator chamber, and, wherein the a reformable gas contacting surface of the reforming catalyst support comprises at least one discrete passageway formed at least partly integrally in the reforming catalyst support and extending along the length of the reforming catalyst support in the direction of reformable hydrocarbon gas flow forming a reformable gas flow channel, said at least one discrete passageway being in heat communication with means for heating the reformable hydrocarbon gas in said at least one discrete passageway.
21. The electrochemical generator apparatus of claim 20, wherein the reformable gas contacting surface comprises a plurality of discrete passageways disposed adjacent one another in the catalyst support, and further comprising means for directing the reformable gas through the discrete passageways.
22. The electrochemical generator apparatus of claim 20, wherein the means for heating said reformable hydrocarbon gas comprises said spent gas exit or combusted exhaust gas exit is directed in heat communication with a wall of the reforming chamber, wherein the wall of the reforming chamber is disposed around the catalyst support, partly closing the at least one discrete passageway.
23. The electrochemical generator apparatus of claim 21, wherein the reforming catalyst material comprises a catalyst support impregnated with catalyst in which the gas flow channels are formed at least partly by integral slots extending inwardly into the body and elongated in the direction of gas flow.
24. The electrochemical generator apparatus of claim 21, wherein the reforming catalyst material comprises a catalyst support having at least one central passage and at least one integral slot extending inwardly into the body, the central passage and the slot being elongated in the direction of gas flow, and further comprising at least one confining wall disposed around the body, the confining wall partly closing the integral slot.
25. The electrochemical generator apparatus of claim 20, wherein the reforming catalyst support comprises a non-rigid, porous, fibrous alumina support impregnated with catalyst, wherein the fibers are compressible and substantially not sintered, and elongated in the direction of gas flow.
26. The electrochemical generator apparatus of claim 25, wherein the catalyst impregnated on the catalyst support comprises Ni and MgO.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US19871194A | 1994-02-18 | 1994-02-18 | |
US198,711 | 1994-02-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2142781A1 true CA2142781A1 (en) | 1995-08-19 |
Family
ID=22734480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002142781A Abandoned CA2142781A1 (en) | 1994-02-18 | 1995-02-17 | Hydrocarbon reforming catalyst material and configuration of the same |
Country Status (7)
Country | Link |
---|---|
US (1) | US5527631A (en) |
EP (1) | EP0677327B1 (en) |
JP (1) | JPH0822835A (en) |
KR (1) | KR950031230A (en) |
CA (1) | CA2142781A1 (en) |
DE (1) | DE69506767T2 (en) |
TW (1) | TW299345B (en) |
Families Citing this family (114)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4438555C1 (en) * | 1994-10-28 | 1996-03-07 | Mtu Friedrichshafen Gmbh | Fuel cell arrangement with reforming device |
DK175723B1 (en) * | 1995-03-20 | 2005-02-07 | Topsoe Haldor As | Process for producing electrical energy in a high temperature fuel cell |
WO1999010945A1 (en) * | 1997-08-26 | 1999-03-04 | Shell Internationale Research Maatschappij B.V. | Producing electrical energy from natural gas using a solid oxide fuel cell |
US6641625B1 (en) | 1999-05-03 | 2003-11-04 | Nuvera Fuel Cells, Inc. | Integrated hydrocarbon reforming system and controls |
US6440594B1 (en) * | 1999-06-17 | 2002-08-27 | California Institute Of Technology | Aerosol feed direct methanol fuel cell |
US6221522B1 (en) * | 1999-09-10 | 2001-04-24 | Siemens Westinghouse Power Corporation | Open end protection for solid oxide fuel cells |
US6440596B1 (en) | 1999-10-20 | 2002-08-27 | Technology Management, Inc. | Solid-oxide fuel cell hot assembly |
US6489050B1 (en) | 1999-11-01 | 2002-12-03 | Technology Management, Inc. | Apparatus and method for cooling high-temperature fuel cell stacks |
WO2001053196A1 (en) * | 2000-01-21 | 2001-07-26 | Conoco Inc. | Thermal shock resistant catalysts for synthesis gas production |
DE10030775C1 (en) * | 2000-06-23 | 2001-12-20 | Buderus Heiztechnik Gmbh | Fluid dosing method for gas generation device for fuel cell system uses central 3-way mixing valve for pulsed dosing of hydrocarbon and water in alternation |
US6946209B1 (en) | 2000-09-25 | 2005-09-20 | Siemens Westinghouse Power Corporation | Desulfurization for fuel cell systems using sulfur separating membranes |
AU2002218295A1 (en) * | 2000-11-12 | 2002-05-21 | Klaus Rennebeck | Method and device for obtaining hydrogen by means of a catalytic micro-hollow fibre reformer |
US20020122969A1 (en) * | 2000-12-15 | 2002-09-05 | Manfred Herrmann | Pressure driven hermetically sealed pump for fuel cell system |
US7182924B2 (en) * | 2001-03-13 | 2007-02-27 | Corning Incorporated | Substrate packing for monolith reactors |
US6855272B2 (en) * | 2001-07-18 | 2005-02-15 | Kellogg Brown & Root, Inc. | Low pressure drop reforming exchanger |
US7067208B2 (en) * | 2002-02-20 | 2006-06-27 | Ion America Corporation | Load matched power generation system including a solid oxide fuel cell and a heat pump and an optional turbine |
AU2003294103A1 (en) * | 2002-08-07 | 2004-03-19 | Battelle Memorial Institute | Passive vapor exchange systems and techniques for fuel reforming and prevention of carbon fouling |
US20040043900A1 (en) * | 2002-08-12 | 2004-03-04 | Combs Glenn A. | Heterogeneous gaseous chemical reactor catalyst |
US6821663B2 (en) * | 2002-10-23 | 2004-11-23 | Ion America Corporation | Solid oxide regenerative fuel cell |
US20040229108A1 (en) * | 2002-11-08 | 2004-11-18 | Valdez Thomas I. | Anode structure for direct methanol fuel cell |
US7282291B2 (en) * | 2002-11-25 | 2007-10-16 | California Institute Of Technology | Water free proton conducting membranes based on poly-4-vinylpyridinebisulfate for fuel cells |
US6924053B2 (en) * | 2003-03-24 | 2005-08-02 | Ion America Corporation | Solid oxide regenerative fuel cell with selective anode tail gas circulation |
US7045238B2 (en) * | 2003-03-24 | 2006-05-16 | Ion America Corporation | SORFC power and oxygen generation method and system |
US7878280B2 (en) * | 2003-04-09 | 2011-02-01 | Bloom Energy Corporation | Low pressure hydrogen fueled vehicle and method of operating same |
US7364810B2 (en) | 2003-09-03 | 2008-04-29 | Bloom Energy Corporation | Combined energy storage and fuel generation with reversible fuel cells |
US7575822B2 (en) | 2003-04-09 | 2009-08-18 | Bloom Energy Corporation | Method of optimizing operating efficiency of fuel cells |
US7482078B2 (en) * | 2003-04-09 | 2009-01-27 | Bloom Energy Corporation | Co-production of hydrogen and electricity in a high temperature electrochemical system |
US7150927B2 (en) * | 2003-09-10 | 2006-12-19 | Bloom Energy Corporation | SORFC system with non-noble metal electrode compositions |
JP4986378B2 (en) * | 2003-11-26 | 2012-07-25 | 京セラ株式会社 | Fuel cell assembly |
US7569193B2 (en) | 2003-12-19 | 2009-08-04 | Applied Materials, Inc. | Apparatus and method for controlled combustion of gaseous pollutants |
US7422810B2 (en) * | 2004-01-22 | 2008-09-09 | Bloom Energy Corporation | High temperature fuel cell system and method of operating same |
US7364812B2 (en) * | 2004-03-19 | 2008-04-29 | Pittsburgh Electric Engines, Inc. | Multi-function solid oxide fuel cell bundle and method of making the same |
KR100599668B1 (en) * | 2004-08-19 | 2006-07-12 | 한국과학기술연구원 | Catalyst stack for partial oxidation reforming of fuel, apparatus for fuel reforming using the catalyst and method for fuel reforming using the catalyst |
US20060042565A1 (en) * | 2004-08-26 | 2006-03-02 | Eaton Corporation | Integrated fuel injection system for on-board fuel reformer |
US7736599B2 (en) * | 2004-11-12 | 2010-06-15 | Applied Materials, Inc. | Reactor design to reduce particle deposition during process abatement |
US7476616B2 (en) * | 2004-12-13 | 2009-01-13 | Fsi International, Inc. | Reagent activator for electroless plating |
WO2006068319A2 (en) * | 2004-12-22 | 2006-06-29 | Honda Motor Co., Ltd. | Fuel cell system |
US20060147771A1 (en) * | 2005-01-04 | 2006-07-06 | Ion America Corporation | Fuel cell system with independent reformer temperature control |
US7514166B2 (en) * | 2005-04-01 | 2009-04-07 | Bloom Energy Corporation | Reduction of SOFC anodes to extend stack lifetime |
US7524572B2 (en) * | 2005-04-07 | 2009-04-28 | Bloom Energy Corporation | Fuel cell system with thermally integrated combustor and corrugated foil reformer |
US20060251934A1 (en) * | 2005-05-09 | 2006-11-09 | Ion America Corporation | High temperature fuel cell system with integrated heat exchanger network |
US8691462B2 (en) | 2005-05-09 | 2014-04-08 | Modine Manufacturing Company | High temperature fuel cell system with integrated heat exchanger network |
US7858256B2 (en) * | 2005-05-09 | 2010-12-28 | Bloom Energy Corporation | High temperature fuel cell system with integrated heat exchanger network |
US7700210B2 (en) | 2005-05-10 | 2010-04-20 | Bloom Energy Corporation | Increasing thermal dissipation of fuel cell stacks under partial electrical load |
JP2008546525A (en) * | 2005-06-13 | 2008-12-25 | アプライド マテリアルズ インコーポレイテッド | Method and apparatus for detoxifying treatment |
US7520916B2 (en) * | 2005-07-25 | 2009-04-21 | Bloom Energy Corporation | Partial pressure swing adsorption system for providing hydrogen to a vehicle fuel cell |
US20070017368A1 (en) * | 2005-07-25 | 2007-01-25 | Ion America Corporation | Gas separation method and apparatus using partial pressure swing adsorption |
JP5542332B2 (en) | 2005-07-25 | 2014-07-09 | ブルーム エナジー コーポレーション | Fuel cell system that partially recycles anode exhaust |
DK1908144T3 (en) * | 2005-07-25 | 2012-08-13 | Bloom Energy Corp | FUEL CELL SYSTEM WITH ELECTROCHEMICAL ANODE EXHAUST GAS RECYCLING |
US7591880B2 (en) * | 2005-07-25 | 2009-09-22 | Bloom Energy Corporation | Fuel cell anode exhaust fuel recovery by adsorption |
WO2007053626A2 (en) * | 2005-10-31 | 2007-05-10 | Applied Materials, Inc. | Process abatement reactor |
US7655196B2 (en) | 2005-11-16 | 2010-02-02 | Fuelcell Energy, Inc. | Reforming catalyst and method and apparatus for making and loading same |
US7659022B2 (en) | 2006-08-14 | 2010-02-09 | Modine Manufacturing Company | Integrated solid oxide fuel cell and fuel processor |
WO2007087305A2 (en) * | 2006-01-23 | 2007-08-02 | Bloom Energy Corporation | Integrated solid oxide fuel cell and fuel processor |
US9190693B2 (en) | 2006-01-23 | 2015-11-17 | Bloom Energy Corporation | Modular fuel cell system |
WO2007095150A2 (en) * | 2006-02-11 | 2007-08-23 | Applied Materials, Inc. | Methods and apparatus for pfc abatement using a cdo chamber |
US7704617B2 (en) * | 2006-04-03 | 2010-04-27 | Bloom Energy Corporation | Hybrid reformer for fuel flexibility |
US8822094B2 (en) * | 2006-04-03 | 2014-09-02 | Bloom Energy Corporation | Fuel cell system operated on liquid fuels |
JP5154026B2 (en) * | 2006-04-14 | 2013-02-27 | 本田技研工業株式会社 | Fuel cell system |
JP5021229B2 (en) * | 2006-04-14 | 2012-09-05 | 本田技研工業株式会社 | Fuel cell system |
JP5021237B2 (en) * | 2006-05-18 | 2012-09-05 | 本田技研工業株式会社 | Fuel cell system |
JP5021238B2 (en) * | 2006-05-18 | 2012-09-05 | 本田技研工業株式会社 | Fuel cell system |
JP5021236B2 (en) * | 2006-05-18 | 2012-09-05 | 本田技研工業株式会社 | Fuel cell system |
US8241801B2 (en) | 2006-08-14 | 2012-08-14 | Modine Manufacturing Company | Integrated solid oxide fuel cell and fuel processor |
WO2008030394A2 (en) * | 2006-09-06 | 2008-03-13 | Bloom Energy Corporation | Flexible fuel cell system configuration to handle multiple fuels |
US7846600B2 (en) * | 2006-09-21 | 2010-12-07 | Bloom Energy Corporation | Adaptive purge control to prevent electrode redox cycles in fuel cell systems |
US7968245B2 (en) * | 2006-09-25 | 2011-06-28 | Bloom Energy Corporation | High utilization stack |
WO2008048445A2 (en) | 2006-10-18 | 2008-04-24 | Bloom Energy Corporation | Anode with remarkable stability under conditions of extreme fuel starvation |
US10615444B2 (en) | 2006-10-18 | 2020-04-07 | Bloom Energy Corporation | Anode with high redox stability |
WO2008051368A2 (en) * | 2006-10-23 | 2008-05-02 | Bloom Energy Corporation | Dual function heat exchanger for start-up humidification and facility heating in sofc system |
US7393603B1 (en) * | 2006-12-20 | 2008-07-01 | Bloom Energy Corporation | Methods for fuel cell system optimization |
US20090214905A1 (en) * | 2007-01-08 | 2009-08-27 | California Institute Of Technology | Direct methanol fuel cell operable with neat methanol |
US7883803B2 (en) * | 2007-03-30 | 2011-02-08 | Bloom Energy Corporation | SOFC system producing reduced atmospheric carbon dioxide using a molten carbonated carbon dioxide pump |
US7833668B2 (en) * | 2007-03-30 | 2010-11-16 | Bloom Energy Corporation | Fuel cell system with greater than 95% fuel utilization |
WO2008127601A1 (en) | 2007-04-13 | 2008-10-23 | Bloom Energy Corporation | Heterogeneous ceramic composite sofc electrolyte |
US20080254336A1 (en) * | 2007-04-13 | 2008-10-16 | Bloom Energy Corporation | Composite anode showing low performance loss with time |
US7846599B2 (en) | 2007-06-04 | 2010-12-07 | Bloom Energy Corporation | Method for high temperature fuel cell system start up and shutdown |
US8920997B2 (en) | 2007-07-26 | 2014-12-30 | Bloom Energy Corporation | Hybrid fuel heat exchanger—pre-reformer in SOFC systems |
US8852820B2 (en) | 2007-08-15 | 2014-10-07 | Bloom Energy Corporation | Fuel cell stack module shell with integrated heat exchanger |
US8067129B2 (en) | 2007-11-13 | 2011-11-29 | Bloom Energy Corporation | Electrolyte supported cell designed for longer life and higher power |
US9246184B1 (en) | 2007-11-13 | 2016-01-26 | Bloom Energy Corporation | Electrolyte supported cell designed for longer life and higher power |
WO2009105191A2 (en) | 2008-02-19 | 2009-08-27 | Bloom Energy Corporation | Fuel cell system containing anode tail gas oxidizer and hybrid heat exchanger/reformer |
JP5396718B2 (en) * | 2008-02-20 | 2014-01-22 | カシオ計算機株式会社 | POWER GENERATION DEVICE, ITS CONTROL DEVICE, OPERATION METHOD, AND ELECTRONIC DEVICE |
EP2140933A1 (en) | 2008-07-02 | 2010-01-06 | Werner Soyez | Structured catalyst hold for pipe reactors |
US8968958B2 (en) * | 2008-07-08 | 2015-03-03 | Bloom Energy Corporation | Voltage lead jumper connected fuel cell columns |
US9287571B2 (en) * | 2008-07-23 | 2016-03-15 | Bloom Energy Corporation | Operation of fuel cell systems with reduced carbon formation and anode leading edge damage |
WO2010117990A2 (en) * | 2009-04-09 | 2010-10-14 | University Of Miami | Self sustained electrochemical promotion catalysts |
US8617763B2 (en) * | 2009-08-12 | 2013-12-31 | Bloom Energy Corporation | Internal reforming anode for solid oxide fuel cells |
US8445156B2 (en) * | 2009-09-02 | 2013-05-21 | Bloom Energy Corporation | Multi-stream heat exchanger for a fuel cell system |
WO2011094098A2 (en) * | 2010-01-26 | 2011-08-04 | Bloom Energy Corporation | Phase stable doped zirconia electrolyte compositions with low degradation |
US8440362B2 (en) | 2010-09-24 | 2013-05-14 | Bloom Energy Corporation | Fuel cell mechanical components |
US8877399B2 (en) | 2011-01-06 | 2014-11-04 | Bloom Energy Corporation | SOFC hot box components |
JP6041162B2 (en) * | 2012-08-01 | 2016-12-07 | 国立大学法人九州大学 | Paper-like catalyst for reforming hydrocarbons, paper-like catalyst array, and solid oxide fuel cell having paper-like catalyst or paper-like catalyst array |
JP6339582B2 (en) | 2012-11-20 | 2018-06-06 | ブルーム エナジー コーポレーション | Doped scandia stabilized zirconia electrolyte composition |
US9755263B2 (en) | 2013-03-15 | 2017-09-05 | Bloom Energy Corporation | Fuel cell mechanical components |
US9093682B2 (en) | 2013-08-26 | 2015-07-28 | 19 Space Energy, LLC | Reforming chamber with multiple electrodes to generate hydrogen |
WO2015061274A1 (en) | 2013-10-23 | 2015-04-30 | Bloom Energy Corporation | Pre-reformer for selective reformation of higher hydrocarbons |
MX352227B (en) | 2013-11-06 | 2017-11-15 | WATT Fuel Cell Corp | Liquid fuel cpox reformers and methods of cpox reforming. |
JP6253795B2 (en) | 2013-11-06 | 2017-12-27 | ワット・フューエル・セル・コーポレイションWatt Fuel Cell Corp. | Gaseous fuel CPOX reformer and CPOX reforming method |
JP6285563B2 (en) | 2013-11-06 | 2018-02-28 | ワット・フューエル・セル・コーポレイションWatt Fuel Cell Corp. | Reformer with perovskite as structural component |
CA2929886C (en) | 2013-11-06 | 2019-03-05 | WATT Fuel Cell Corp | Integrated gaseous fuel cpox reformer and fuel cell systems, and methods of producing electricity |
US10106406B2 (en) | 2013-11-06 | 2018-10-23 | Watt Fuel Cell Corp. | Chemical reactor with manifold for management of a flow of gaseous reaction medium thereto |
JP6549600B2 (en) | 2013-11-06 | 2019-07-24 | ワット・フューエル・セル・コーポレイションWatt Fuel Cell Corp. | Liquid fuel CPOX reformer and fuel cell integrated system and method of generating electricity |
WO2015123304A1 (en) | 2014-02-12 | 2015-08-20 | Bloom Energy Corporation | Structure and method for fuel cell system where multiple fuel cells and power electronics feed loads in parallel allowing for integrated electrochemical impedance spectroscopy ("eis") |
US10096840B1 (en) | 2014-12-15 | 2018-10-09 | Bloom Energy Corporation | High temperature air purge of solid oxide fuel cell anode electrodes |
CA2978250C (en) * | 2015-03-05 | 2023-09-26 | Watt Fuel Cell Corp. | Afterburners including methods of making and operating |
US10651496B2 (en) | 2015-03-06 | 2020-05-12 | Bloom Energy Corporation | Modular pad for a fuel cell system |
WO2016154198A1 (en) | 2015-03-24 | 2016-09-29 | Bloom Energy Corporation | Perimeter electrolyte reinforcement layer composition for solid oxide fuel cell electrolytes |
WO2018049212A1 (en) * | 2016-09-09 | 2018-03-15 | Fuelcell Energy, Inc. | Molten carbonate fuel cell stack having direct and indirect internal reformers |
US10361442B2 (en) | 2016-11-08 | 2019-07-23 | Bloom Energy Corporation | SOFC system and method which maintain a reducing anode environment |
KR102331593B1 (en) * | 2017-03-02 | 2021-11-26 | 로드리고 코키스 산체스-꼰샤 | Hydrodynamic systems for optimizing the performance of catalytic alloys and improving microbial contaminant removal properties of hydrocarbons |
US10680251B2 (en) | 2017-08-28 | 2020-06-09 | Bloom Energy Corporation | SOFC including redox-tolerant anode electrode and system including the same |
US11398634B2 (en) | 2018-03-27 | 2022-07-26 | Bloom Energy Corporation | Solid oxide fuel cell system and method of operating the same using peak shaving gas |
DE102020202875A1 (en) | 2020-03-06 | 2021-09-09 | Robert Bosch Gesellschaft mit beschränkter Haftung | Fuel cell device |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2408164A (en) * | 1942-04-25 | 1946-09-24 | Phillips Petroleum Co | Catalyst preparation |
US4407785A (en) * | 1972-11-28 | 1983-10-04 | Engelhard Corporation | Method of conducting catalytically promoted gas-phase reactions |
US4233187A (en) * | 1979-03-26 | 1980-11-11 | United Catalysts Inc. | Catalyst and process for steam-reforming of hydrocarbons |
EP0025308B1 (en) * | 1979-09-06 | 1984-07-11 | Imperial Chemical Industries Plc | A process and apparatus for catalytically reacting steam with a hydrocarbon in endothermic conditions |
EP0045126B1 (en) * | 1980-06-25 | 1984-12-05 | Imperial Chemical Industries Plc | Catalytic process for producing hydrogen |
US4328130A (en) * | 1980-10-22 | 1982-05-04 | Chevron Research Company | Shaped channeled catalyst |
US4395468A (en) * | 1980-12-22 | 1983-07-26 | Westinghouse Electric Corp. | Fuel cell generator |
US4490444A (en) * | 1980-12-22 | 1984-12-25 | Westinghouse Electric Corp. | High temperature solid electrolyte fuel cell configurations and interconnections |
JPS61267272A (en) * | 1985-05-22 | 1986-11-26 | Hitachi Ltd | Molten carbonate type fuel cell |
JPS6280971A (en) * | 1985-10-02 | 1987-04-14 | Hitachi Ltd | Internal reform catalyst material for fuel cell and its manufacture |
GB8528031D0 (en) * | 1985-11-13 | 1985-12-18 | Ici Plc | Ceramic structures |
DE3611732A1 (en) * | 1986-04-08 | 1987-10-15 | Kernforschungsz Karlsruhe | METHOD FOR PRODUCING CATALYST SUPPORT BODIES AND CATALYST SUPPORT BODY PRODUCED THEREOF |
US4729931A (en) * | 1986-11-03 | 1988-03-08 | Westinghouse Electric Corp. | Reforming of fuel inside fuel cell generator |
US4751152A (en) * | 1987-04-06 | 1988-06-14 | Westinghouse Electric Corp. | High bulk self-supporting electrode with integral gas feed conduit for solid oxide fuel cells |
US4898792A (en) * | 1988-12-07 | 1990-02-06 | Westinghouse Electric Corp. | Electrochemical generator apparatus containing modified high temperature insulation and coated surfaces for use with hydrocarbon fuels |
US4885078A (en) * | 1988-12-07 | 1989-12-05 | Westinghouse Electric Corp. | Devices capable of removing silicon and aluminum from gaseous atmospheres |
JPH0755802B2 (en) * | 1989-09-22 | 1995-06-14 | 日本碍子株式会社 | Fuel reformer for fuel cell system |
US4983471A (en) * | 1989-12-28 | 1991-01-08 | Westinghouse Electric Corp. | Electrochemical cell apparatus having axially distributed entry of a fuel-spent fuel mixture transverse to the cell lengths |
US5143800A (en) * | 1990-07-25 | 1992-09-01 | Westinghouse Electric Corp. | Electrochemical cell apparatus having combusted exhaust gas heat exchange and valving to control the reformable feed fuel composition |
US5047299A (en) * | 1990-07-25 | 1991-09-10 | Westinghouse Electric Corp. | Electrochemical cell apparatus having an integrated reformer-mixer nozzle-mixer diffuser |
US5169730A (en) * | 1990-07-25 | 1992-12-08 | Westinghouse Electric Corp. | Electrochemical cell apparatus having an exterior fuel mixer nozzle |
US5082751A (en) * | 1990-10-18 | 1992-01-21 | Westinghouse Electric Corp. | Internal natural gas reformer-dividers for a solid oxide fuel cell generator configuration |
US5250489A (en) * | 1990-11-26 | 1993-10-05 | Catalytica, Inc. | Catalyst structure having integral heat exchange |
-
1995
- 1995-02-08 TW TW084101050A patent/TW299345B/zh active
- 1995-02-14 DE DE69506767T patent/DE69506767T2/en not_active Expired - Fee Related
- 1995-02-14 EP EP95300927A patent/EP0677327B1/en not_active Expired - Lifetime
- 1995-02-17 KR KR1019950002986A patent/KR950031230A/en not_active Application Discontinuation
- 1995-02-17 CA CA002142781A patent/CA2142781A1/en not_active Abandoned
- 1995-02-20 JP JP7056675A patent/JPH0822835A/en not_active Withdrawn
- 1995-10-04 US US08/539,814 patent/US5527631A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE69506767T2 (en) | 1999-05-20 |
EP0677327B1 (en) | 1998-12-23 |
DE69506767D1 (en) | 1999-02-04 |
US5527631A (en) | 1996-06-18 |
TW299345B (en) | 1997-03-01 |
EP0677327A1 (en) | 1995-10-18 |
KR950031230A (en) | 1995-12-18 |
JPH0822835A (en) | 1996-01-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5527631A (en) | Hydrocarbon reforming catalyst material and configuration of the same | |
US5082751A (en) | Internal natural gas reformer-dividers for a solid oxide fuel cell generator configuration | |
CA2041726C (en) | Electrochemical cell apparatus having an exterior fuel mixer nozzle | |
US4983471A (en) | Electrochemical cell apparatus having axially distributed entry of a fuel-spent fuel mixture transverse to the cell lengths | |
US5601937A (en) | Hydrocarbon reformer for electrochemical cells | |
EP0242200B1 (en) | Fuel cell generators | |
US5047299A (en) | Electrochemical cell apparatus having an integrated reformer-mixer nozzle-mixer diffuser | |
JP2965273B2 (en) | Electrochemical cell device with a valve for controlling the composition of the reformable fuel gas | |
EP0264688B1 (en) | Fuel cell generator containing self-supporting high gas flow solid oxide electrolyte fuel cells | |
US5858314A (en) | Thermally enhanced compact reformer | |
CA1304581C (en) | Compact hydrogen generator | |
US20030054222A1 (en) | Fuel cell | |
US7517507B2 (en) | Steam reformer | |
US7078120B2 (en) | Fuel cell | |
EP0938756A1 (en) | A hydrocarbon reformer for electrochemical cells | |
JP2022170259A (en) | fuel cell system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |