WO1998055227A1 - Partial oxidation catalyst - Google Patents

Partial oxidation catalyst Download PDF

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Publication number
WO1998055227A1
WO1998055227A1 PCT/US1998/010523 US9810523W WO9855227A1 WO 1998055227 A1 WO1998055227 A1 WO 1998055227A1 US 9810523 W US9810523 W US 9810523W WO 9855227 A1 WO9855227 A1 WO 9855227A1
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Prior art keywords
catalyst
oxide
ion conducting
hydrocarbon fuel
ceramic
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PCT/US1998/010523
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French (fr)
Inventor
Michael Krumpelt
Shabbir Ahmed
Romesh Kumar
Rajiv Doshi
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University of Chicago
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University of Chicago
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Priority to EP98922483A priority Critical patent/EP0939672A4/en
Priority to JP11502514A priority patent/JP2000505725A/en
Publication of WO1998055227A1 publication Critical patent/WO1998055227A1/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—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
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • 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
    • 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
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1619—Measuring the temperature
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Fuel cell-powered vehicles are being developed by the domestic and foreign automotive industry as a more fuel efficient and less polluting alternative to the current internal combustion engines. Since the fuel cells operate preferably on hydrogen, but storing of hydrogen on-board a vehicle is not as convenient as carrying liquid hydrocarbon fuel in a tank, a "fuel processor" must generate the hydrogen.
  • Converting hydrocarbon fuels to hydrogen can be done by steam reforming (reaction of the hydrocarbon with steam) or by partial oxidation (reaction with a substoichiometric amount of air).
  • Steam reforming reactors are fairly bulky and are heat-transfer limited. Partial oxidation is more rapid but less developed. See U.S. patent no. 5,248,566 issued September 28, 1993 to Kumar et al., the disclosure of which is incorporated by reference, for a general discussion of the use of a fuel cell in a vehicle.
  • This invention relates to a new family of catalysts that are effective for the conversion of a wide range of hydrocarbons, incuding aliphatic hydrocarbons to hydrogen.
  • This invention relates to a partial oxidation catalyst. More specifically, this invention relates to a catalyst for partially oxidizing hydrocarbon fuels such as gasoline to produce a high percentage yield of hydrogen suitable for supplying a fuel cell.
  • hydrocarbons e.g. n-octane, iso-octane, etc.
  • the difficulty of converting hydrocarbons (e.g. n-octane, iso-octane, etc.), a main component of gasoline, to hydrogen is the fact that the hydrogen/oxygen bond is thermodynamically stronger than the carbon oxygen bond at moderate temperatures. Under thermal equilibrium conditions, the reaction products will therefore be rich in water and poor in hydrogen.
  • a bifunctional catalyst is required which can "dehydrogenate" the hydrocarbon molecule, and then selectively oxidize the carbon chain.
  • the catalyst is a cermet containing ceria as the oxide ion conduction material, and platinum as the hydrogen dissolving material.
  • the catalyst can be prepared from a high surface area powder of doped ceria and a second phase powder which could be either a metal like platinum or an oxide like Co 2 0 3 which is reduced in-situ in the reactor to cobalt metal.
  • Other metals include all noble and transition metals.
  • oxide ion conducting materials such as zirconia, bismuth oxides or vanadates, lanthanum gallate, perovskite containing manganese, iron, cobalt, or others forming oxygen deficient structures are applicable.
  • alkanes can be oxidized by contact with the catalyst of the present invention to form alkene oxides, ketones or aldehydes.
  • FIGURE 1 is a graph depicting the relationship between temperature and product gas composition for regular gasoline and a catalyst of Pt/CeGdO.
  • FIG. 2 is a graph depicting the relationship between temperature and product gas composition for premium gasoline and a catalyst of Pt/CeGdO.
  • FIG. 3 is a graph depicting the relationship between temperature and product gas composition for premium gasoline and a catalyst of Pt/CeSmLiO.
  • FIG. 4 is a graph depicting the relationship between temperature and product gas composition for natural gas and a catalyst of Pt/CeGdO.
  • the difficulty of converting hydrocarbons such as n-octane (the main component of gasoline) to hydrogen is the fact that the hydrogen/oxygen bond is thermodynamically stronger than the carbon oxygen bond at moderate temperatures. Under thermal equilibrium conditions, the reaction product will therefore be rich in water and poor in hydrogen.
  • a catalyst that can "dyhydrogenate" the hydrocarbon molecule, and then selectively oxidize the carbon chain. Thus, the catalyst must be bifunctional.
  • metals that dissolve hydrogen such as platinum, nickel or any Group VIII metal. Ni is the least preferred because an oxidation product thereof, Ni0 4 , is poisonous.
  • Sources of ionic oxygen are oxides crystallizing in the fluorite or perovskite structure, such as for instance by way of example without limitation, Zr0 2 , Ce0 2 , Bi 2 0 3 , BiV0 4 , LaGa0 3 .
  • cermet containing the catalysts were prepared by a solid state method.
  • the starting powders were a high surface area (about 32 m 2 /gm) doped ceria (Ce 8 Gd ⁇ 2 0 1 -9 ) and a second phase.
  • the starting second phase powder was either a metal like Pt or an oxide like Co 2 0 3 which is reduced in-situ in the reactor to cobalt metal.
  • the two powders were mixed in the desired ratios of 1% pt metal and 99 % ceramic along with some isopropyl alcohol and up to 5 wt% of a dispersing agent for the second phase (oleic acid for metals and Hypermer Kd2 from ICI Americas Inc. for oxides) and then milled vigorously in a high density polyethylene bottle with Tosoh milling media.
  • the mixture was then dried to remove the alcohol while stirring on a hot plate to about 70°C, pressed into 1.125-1.5" pellets with about 3 gms of powder using 10,000 to 12,000 lbs. load and fired at 1000°C for 15- 60 mins. in air.
  • the resulting pellet had a uniform pore structure to allow gas access.
  • Such catalysts were tested in a reactor with feed streams of a hydrocarbon fuel (C n H , water and oxygen.
  • a hydrocarbon fuel C n H , water and oxygen.
  • the liquid fuel and liquid water were vaporized in a heated coil under a temperature bath maintained at 130-140°C.
  • Oxygen was mixed in with the vapors and the reactant mixture was then fed into the reactor tube.
  • the three feeds were mixed such that the (oxygen/fuel) molar ratio was less than or equal to n/2, while the water/fuel (molar) ratio was greater than or equal to n.
  • the feed rates were adjusted to obtain a residence time of between 0.1-2 second in contact with the catalysts.
  • the catalysts particles were packed inside the reactor, typically weighing 1.5-2.5 g and occupying 1-3 cm 3 of space.
  • the reactor tube was kept in an electrically heated furnace and maintained at the desired temperature (200-700°C).
  • Thermocouples located above and below the catalyst measured the temperature at the catalyst bed inlet and outlet, respectively.
  • Fig. 1 there is reported the results of tests using a Pt/CeGdO two part catalyst with regular gasoline.
  • Fig. 2 shows the results of tests using a Pt/Ce GdO two part catalyst with premium gasoline.
  • Fig. 3 shows the results of tests using a Pt/Ce Sm LiO two part catalyst with premium gasoline and
  • Fig. 4 shows the results of Pt/CeGdO two part catalyst on natural gas.
  • any Group VIII metal may be used in combination with an oxide-ion conducting ceramic crystallizing in the fluorite or perovskite structure.
  • the oxide may be doped with a suitable rare earth, such as Gd or Sm or additionally with a suitable alkali or alkaline earth metal, such as Li or Na.
  • the reaction which is exothermic, should be conducted in the range of from about 400°C to about 900°C and preferably from about 500°C to about 750°C.
  • various alkanes such as ethane
  • the reaction has to be at a temperature and for a time sufficient to form the desired products, all parameters of time and temperature are within the skill of art.

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Abstract

A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400 °C for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also diclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Description

PARTIAL OXIDATION CATALYST
CONTRACTUAL ORIGIN OF THE INVENTION
The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy (DOE)and The University of Chicago representing Argonne National Laboratory.
Background Of The Invention Fuel cell-powered vehicles are being developed by the domestic and foreign automotive industry as a more fuel efficient and less polluting alternative to the current internal combustion engines. Since the fuel cells operate preferably on hydrogen, but storing of hydrogen on-board a vehicle is not as convenient as carrying liquid hydrocarbon fuel in a tank, a "fuel processor" must generate the hydrogen.
Converting hydrocarbon fuels to hydrogen can be done by steam reforming (reaction of the hydrocarbon with steam) or by partial oxidation (reaction with a substoichiometric amount of air). Steam reforming reactors are fairly bulky and are heat-transfer limited. Partial oxidation is more rapid but less developed. See U.S. patent no. 5,248,566 issued September 28, 1993 to Kumar et al., the disclosure of which is incorporated by reference, for a general discussion of the use of a fuel cell in a vehicle.
It is highly desirable to provide a catalyst for the partial oxidation reaction so that the temperature, can be lowered from the 1000°C temperatures required for steam reformers. At lower temperatures, the reactors can be smaller, and the product gas contains higher concentrations of hydrogen and less carbon monoxide, which is desirable. However, an appropriate catalyst has heretofore not been available. This invention relates to a new family of catalysts that are effective for the conversion of a wide range of hydrocarbons, incuding aliphatic hydrocarbons to hydrogen.
Summary of the Invention
This invention relates to a partial oxidation catalyst. More specifically, this invention relates to a catalyst for partially oxidizing hydrocarbon fuels such as gasoline to produce a high percentage yield of hydrogen suitable for supplying a fuel cell. The difficulty of converting hydrocarbons (e.g. n-octane, iso-octane, etc.), a main component of gasoline, to hydrogen is the fact that the hydrogen/oxygen bond is thermodynamically stronger than the carbon oxygen bond at moderate temperatures. Under thermal equilibrium conditions, the reaction products will therefore be rich in water and poor in hydrogen. In order to produce a hydrogen- rich gas, a bifunctional catalyst is required which can "dehydrogenate" the hydrocarbon molecule, and then selectively oxidize the carbon chain.
In one aspect of the invention, the catalyst is a cermet containing ceria as the oxide ion conduction material, and platinum as the hydrogen dissolving material. The catalyst can be prepared from a high surface area powder of doped ceria
Figure imgf000004_0001
and a second phase powder which could be either a metal like platinum or an oxide like Co203 which is reduced in-situ in the reactor to cobalt metal. Other metals include all noble and transition metals. Other oxide ion conducting materials such as zirconia, bismuth oxides or vanadates, lanthanum gallate, perovskite containing manganese, iron, cobalt, or others forming oxygen deficient structures are applicable.
In another aspect of the invention, various alkanes can be oxidized by contact with the catalyst of the present invention to form alkene oxides, ketones or aldehydes.
Brief Description of the Drawings
The invention consists of certain novel features and a combination of parts hereinafter fully described, illustrated in the accompanying drawings, and particularly pointed out in the appended claims, it being understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention.
FIGURE 1 is a graph depicting the relationship between temperature and product gas composition for regular gasoline and a catalyst of Pt/CeGdO.
FIG. 2 is a graph depicting the relationship between temperature and product gas composition for premium gasoline and a catalyst of Pt/CeGdO.
FIG. 3 is a graph depicting the relationship between temperature and product gas composition for premium gasoline and a catalyst of Pt/CeSmLiO. FIG. 4 is a graph depicting the relationship between temperature and product gas composition for natural gas and a catalyst of Pt/CeGdO. Detailed Description of the Invention
The difficulty of converting hydrocarbons such as n-octane (the main component of gasoline) to hydrogen is the fact that the hydrogen/oxygen bond is thermodynamically stronger than the carbon oxygen bond at moderate temperatures. Under thermal equilibrium conditions, the reaction product will therefore be rich in water and poor in hydrogen. We discovered that in order to get a hydrogen-rich gas one would have to find a catalyst that can "dyhydrogenate" the hydrocarbon molecule, and then selectively oxidize the carbon chain. Thus, the catalyst must be bifunctional. To dehydrogenate a hydrocarbon molecule, one can use metals that dissolve hydrogen such as platinum, nickel or any Group VIII metal. Ni is the least preferred because an oxidation product thereof, Ni04, is poisonous. To selectively oxidize the carbon chain, we found that one is able to use a source of ionic oxygen. Ionic oxygen apparently reacts with the double bonds of a dehydrogenated hydrocarbon to form oxygen carbon bonds. Sources of ionic oxygen are oxides crystallizing in the fluorite or perovskite structure, such as for instance by way of example without limitation, Zr02, Ce02, Bi203, BiV04, LaGa03. By combining such oxides with a hydrogen dissolving metal and passing a hydrocarbon/air mixture over it, we discovered it is possible to obtain hydrogen-rich gas from an aliphatic as well as aromatic hydrocarbons.
We chose for purposes of examples, only, ceria as the oxide ion conducting material, and platinum as the hydrogen dissolving metal. A cermet containing the catalysts were prepared by a solid state method. The starting powders were a high surface area (about 32 m2/gm) doped ceria (Ce 8Gdα201 -9) and a second phase. The starting second phase powder was either a metal like Pt or an oxide like Co203 which is reduced in-situ in the reactor to cobalt metal.
The two powders were mixed in the desired ratios of 1% pt metal and 99 % ceramic along with some isopropyl alcohol and up to 5 wt% of a dispersing agent for the second phase (oleic acid for metals and Hypermer Kd2 from ICI Americas Inc. for oxides) and then milled vigorously in a high density polyethylene bottle with Tosoh milling media. The mixture was then dried to remove the alcohol while stirring on a hot plate to about 70°C, pressed into 1.125-1.5" pellets with about 3 gms of powder using 10,000 to 12,000 lbs. load and fired at 1000°C for 15- 60 mins. in air. The resulting pellet had a uniform pore structure to allow gas access.
Such catalysts were tested in a reactor with feed streams of a hydrocarbon fuel (CnH , water and oxygen. The liquid fuel and liquid water were vaporized in a heated coil under a temperature bath maintained at 130-140°C. Oxygen was mixed in with the vapors and the reactant mixture was then fed into the reactor tube. The three feeds were mixed such that the (oxygen/fuel) molar ratio was less than or equal to n/2, while the water/fuel (molar) ratio was greater than or equal to n. The feed rates were adjusted to obtain a residence time of between 0.1-2 second in contact with the catalysts.
The catalysts particles were packed inside the reactor, typically weighing 1.5-2.5 g and occupying 1-3 cm3 of space. The reactor tube was kept in an electrically heated furnace and maintained at the desired temperature (200-700°C). Thermocouples located above and below the catalyst measured the temperature at the catalyst bed inlet and outlet, respectively.
Referring to Fig. 1 , there is reported the results of tests using a Pt/CeGdO two part catalyst with regular gasoline. Fig. 2 shows the results of tests using a Pt/Ce GdO two part catalyst with premium gasoline. Fig. 3 shows the results of tests using a Pt/Ce Sm LiO two part catalyst with premium gasoline and
Fig. 4 shows the results of Pt/CeGdO two part catalyst on natural gas.
In general, any Group VIII metal (or mixtures thereof) may be used in combination with an oxide-ion conducting ceramic crystallizing in the fluorite or perovskite structure. The oxide may be doped with a suitable rare earth, such as Gd or Sm or additionally with a suitable alkali or alkaline earth metal, such as Li or Na.
In general, the reaction, which is exothermic, should be conducted in the range of from about 400°C to about 900°C and preferably from about 500°C to about 750°C. The lower the temperature while maintaining high H2 concentration and low CO concentration, the better. It is important to obtain as high a concentration of hydrogen as possible, but one limiting aspect is the amount of CO found, which should preferably not exceed 5% by volume. In another aspect of the invention, various alkanes, such as ethane, can be contacted with the inventive catalysts to form various oxides, such as ethylene oxide, ketones and aldehydes. The reaction has to be at a temperature and for a time sufficient to form the desired products, all parameters of time and temperature are within the skill of art.
While there has been disclosed what is considered to be the preferred embodiment of the present invention, it is understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A two-part catalyst comprising a dehydrogenation portion and an oxide -ion conducting portion.
2. The catalyst of claim 1 , wherein the dehydrogenation portion includes a group VIII metal.
3. The catalyst of claim 1 , wherein the dehydrogenation portion is selected from Pt, Pd and mixtures thereof.
4. The catalyst of claim 1 , wherein the dehydrogenation portion includes a group VIII metal other than Ni.
5. The catalyst of claim 4, wherein the oxide-ion conducting portion is a ceramic oxide doped with an acceptable rare earth.
6. The catalyst of claim 5, wherein the ceramic oxide is doped with Gd, Sm or mixtures thereof and an acceptable alkali or alkaline earth metal.
7. The catalyst of claim 1 , wherein the oxide-ion conducting portion is a ceramic oxide selected from the group consisting of Zr02, Ce02, Bi203, (BiVO)4, LaGa03 and mixtures thereof.
8. The catalyst of claim 7, wherein said two-part catalyst is effective at temperatures greater than about 400°C to produce a hydrogen-rich gas from a hydrocarbon fuel in contact therewith wherein the CO content is not greater than about 5% by volume.
9. The catalyst of claim 7, wherein said two-part catalyst is effective at temperatures between about 500°C and about 900°C to produce a hydrogen-rich gas from a hydrocarbon fuel in contact therewith having a CO content not greater than about 5% by volume.
10. The catalyst of claim 7, wherein said two-part catalyst is effective at temperatures in the range of from about 500°C to about 900°C to produce a hydrogen-rich gas from a hydrocarbon fuel in contact therewith, said hydrocarbon fuel being selected from gasoline, natural gas, gas rich in alkanes, gas containing branched alkanes and alkanes.
11. A two-part catalyst comprising a dehydrogenation portion selected from group VIII metals and mixtures thereof, and an oxide -ion conducting portion.
12. The catalyst of claim 11 , wherein Ni is excluded.
13. The catalyst of claim 11 , wherein the group VIII metal is Pt, Pd or mixtures thereof.
14. The catalyst of claim 12, wherein the oxide-ion conducting portion includes a ceramic.
15. The catalyst of claim 14, wherein the ceramic includes one or more of Zr02, Ce02, Bi203, (BiVO)403, LaGa03.
16. The catalyst of claim 15, wherein the ceramic is doped with a rare earth metal.
17. The catalyst of claim 16, wherein the rare earth metal doped ceramic is also doped with an alkali metal or an alkaline earth metal.
18. The catalyst of claim 13, wherein the group VIII metal is Pt and the oxide-ion conducting portion includes Ce02.
19. The catalyst of claim 18, wherein the Ce02 is doped with a rare earth metal.
20. The catalyst of claim 19, wherein the Ce02 doped catalyst is Ce08
Figure imgf000009_0001
21. The catalyst of claim 11 , wherein the group VIII metal is Pd.
22. The catalyst of claim 21 , wherein the oxide-ion conducting portion includes a ceramic including one or more of Zr02, Ce02, Bi203 (V+Bi)203 and
LaGa03.
23. A two-part catalyst comprising a dehydrogenation portion and an oxide -ion conducting portion selected from a ceramic oxide crystallizing in the fluorite or perovskite structure.
24. The catalyst of claim 23, wherein said oxide-ion conducting ceramic is one or more of Zr02, Ce02, Bi203, (BiVO)4, and LaGa03.
25. A method of forming a hydrogen rich gas from a source of hydrocarbon fuel, comprising contacting the hydrocarbon fuel with a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400°C for a time sufficient to generate the hydrogen rich gas while maintaining the CO content less than about 5 volume percent.
26. The method of claim 25, wherein the hydrocarbon fuel is natural gas.
27. The method of claim 25, wherein the hydrocarbon fuel is gasoline.
28. The method of claim 25, wherein the hydrocarbon fuel includes alkanes.
29. The method of claim 28, wherein the hydrocarbon fuel also includes aromatics.
30. The method of claim 29, wherein the hydrocarbon fuel includes branched alkanes and alkenes.
31. The method of claim 26, wherein the dehydrogenation portion includes a group VIM metal, and the oxide-ion conducting portion is selected from a ceramic oxide from the group crystallizing in the fluorite or perovskite structure and mixtures thereof.
32. A method of forming partially oxidized hydrocarbons from ethanes comprising contacting ethane gas with a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.
33. The method of claim 32, wherein the fuel is ethane and the product is ethylene oxide.
34. The method of claim 32, wherein the fuel is an alkane and the product is a ketone or aldehyde or mixtures thereof.
AMENDED CLAIMS
[received by the International Bureau on 16 November 1998 (16.11.98); original claims 16,17 and 32-34 cancelled; original claims 5-7,15,22-24 and 31 amended; remaining claims unchanged (3 pages)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A two-part catalyst comprising a dehydrogenation portion and an oxide -ion conducting portion.
2. The catalyst of claim 1 , wherein the dehydrogenation portion includes a group Vill metal.
3. The catalyst of claim 1 , wherein the dehydrogenation portion is selected from Pt, Pd and mixtures thereof.
4. The catalyst of claim 1 , wherein the dehydrogenation portion includes a group VIII metal other than Ni.
5. The catalyst of claim 4, wherein the oxide-ion conducting portion is a ceramic oxide doped a rare earth.
6. The catalyst of claim 5, wherein the ceramic oxide is doped with Gd, Sm or mixtures thereof and an alkali or alkaline earth metal.
7. The catalyst of claim 1 , wherein the oxide-ion conducting portion includes a ceramic oxide selected from the group consisting of Zr02, Ce02, Bi203, (BiVO)4, LaGaOg and mixtures thereof and a dopant selected from rare earths, the alkaline earth and alkali metals.
8. The catalyst of claim 7, wherein said two-part catalyst is effective at temperatures greater than about 400°C to produce a hydrogen-rich gas from a hydrocarbon fuel in contact therewith wherein the CO content is not greater than about 5% by volume.
9. The catalyst of claim 7, wherein said two-part catalyst is effective at temperatures between about 500°C and about 900°C to produce a hydrogen-rich gas from a hydrocarbon fuel in contact therewith having a CO content not greater than about 5% by volume.
10. The catalyst of claim 7, wherein said two-part catalyst is effective at temperatures in the range of from about 500°C to about 900°C to produce a hydrogen-rich gas from a hydrocarbon fuel in contact therewith, said hydrocarbon fuel being selected from gasoline, natural gas, gas rich in alkanes, gas containing branched alkanes and alkanes.
11. A two-part catalyst comprising a dehydrogenation portion selected from group VIII metals and mixtures thereof, and an oxide -ion conducting portion.
12. The catalyst of claim 11 , wherein Ni is excluded.
13. The catalyst of claim 11 , wherein the group VIII metal is Pt, Pd or mixtures thereof.
14. The catalyst of claim 12, wherein the oxide-ion conducting portion includes a ceramic.
15. The catalyst of claim 14, wherein the ceramic includes one or more of Zr02, Ce02, Bi203, (BiVO)403, LaGa03 and a dopant selected from rare earths, the alkaline earth and alkali metals.
Cancel claim 16. Cancel claim 17.
18. The catalyst of claim 13, wherein the group VIII metal is Pt and the oxide-ion conducting portion includes Ce02.
19. The catalyst of claim 18, wherein the Ce02 is doped with a rare earth metal.
20. The catalyst of claim 19, wherein the Ce02 doped catalyst is Ce08
Gd0.2 01.9-
21. The catalyst of claim 11 , wherein the group VIII metal is Pd.
22. The catalyst of claim 21 , wherein the oxide-ion conducting portion includes a ceramic including one or more of Zr02, Ce02, Bi203 (V+Bi)203 and LaGa03 and a dopant selected from rare earths, the alkaline earth and alkali metals.
23. A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion selected from a ceramic oxide crystallizing in the fluorite structure or LaGa03.
24. The catalyst of claim 23, wherein said oxide-ion conducting ceramic is one or more of Zr02, Ce02, Bi203, (BiVO)4 and a dopant selected from rare earths, the alkaline earth and alkali metals.
25. A method of forming a hydrogen rich gas from a source of hydrocarbon fuel, comprising contacting the hydrocarbon fuel with a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400°C for a time sufficient to generate the hydrogen rich gas while maintaining the CO content less than about 5 volume percent.
26. The method of claim 25, wherein the hydrocarbon fuel is natural gas.
27. The method of claim 25, wherein the hydrocarbon fuel is gasoline.
28. The method of claim 25, wherein the hydrocarbon fuel includes alkanes.
29. The method of claim 28, wherein the hydrocarbon fuel also includes aromatics.
30. The method of claim 29, wherein the hydrocarbon fuel includes branched alkanes and alkenes.
31. The method of claim 26, wherein the dehydrogenation portion includes a group VIII metal, and the oxide-ion conducting portion is selected from a ceramic oxide from the group crystallizing in the fluorite structure or LaGa03 and mixtures thereof.
Cancel claim 32. Cancel claim 33. Cancel claim 34.
STATEMENT UNDER ARTICLE 19
The claims are amended to conform to the claims of corresponding U.S. patent application serial no. 08/867,556 filed June 2, 1997 and application serial no. 09/092,190 filed June 5, 1998, which is a divisional of the prior filed '556 application.
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