+

WO2002066370A2 - Catalyseurs de reformage et procedes de reformage d'alcools a la vapeur - Google Patents

Catalyseurs de reformage et procedes de reformage d'alcools a la vapeur Download PDF

Info

Publication number
WO2002066370A2
WO2002066370A2 PCT/US2002/004527 US0204527W WO02066370A2 WO 2002066370 A2 WO2002066370 A2 WO 2002066370A2 US 0204527 W US0204527 W US 0204527W WO 02066370 A2 WO02066370 A2 WO 02066370A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
methanol
reactor
steam reforming
alcohol
Prior art date
Application number
PCT/US2002/004527
Other languages
English (en)
Other versions
WO2002066370A3 (fr
Inventor
Yong Wang
Anna Lee Y. Tonkovich
Jianli Hu
Ya-Huei Chin
Robert A. Dagle
Chunshe Cao
Original Assignee
Battelle Memorial Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US09/788,294 external-priority patent/US6936237B2/en
Priority claimed from US10/076,881 external-priority patent/US7335346B2/en
Application filed by Battelle Memorial Institute filed Critical Battelle Memorial Institute
Publication of WO2002066370A2 publication Critical patent/WO2002066370A2/fr
Publication of WO2002066370A3 publication Critical patent/WO2002066370A3/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/063—Refinery processes
    • C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • 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
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • 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
    • 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
    • C01B2203/1076—Copper or zinc-based 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • 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
    • C01B2203/1217—Alcohols
    • 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
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • 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
    • C01B2203/1604—Starting up the process
    • 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
    • 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
    • C01B2203/1642—Controlling the product
    • C01B2203/1647—Controlling the amount of the product
    • C01B2203/1652—Measuring the amount of product
    • 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
    • C01B2203/1642—Controlling the product
    • C01B2203/1671—Controlling the composition of the product
    • C01B2203/1676—Measuring the composition of the product
    • 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
    • C01B2203/169—Controlling the feed
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention to catalysts and methods of steam reforming alcohols
  • H 2 hydrogen gas
  • PEMFCs polymer electrolyte membrane fuel cells
  • C0 2 carbon dioxide
  • current technology does not offer economically attractive options for storage of enough hydrogen gas to deliver the driving range to which motorists are accustomed.
  • vehicles could carry a tank of liquid fuel such as an alcohol.
  • the alcohol typically methanol, would pass through a fuel processor that converts the methanol to hydrogen gas that immediately passes to the fuel cell. In this fashion, hydrogen-powered vehicles need not carry any hydrogen tanks.
  • the present invention provides catalysts of at least 4 types: (1) palladium on zinc oxide (Pd ZnO) on a large pore support (Pd/ZnO/support); (2) palladium-ruthenium or palladium-zinc alloy on alumina or zircoma (Pd-Ru or Pd-Zn/Al 2 0 3 or Zr0 2 ); (3) a catalyst comp ⁇ sing copper, zinc, palladium or ruthenium on a ce ⁇ um promoted alumina or zircoma support; and (4) Pd on ZnO on a metal oxide support, characterized by a hydrogen productivity of at least 10,000 ml H 2 /ml cat hr, when tested according to the procedure set forth in the Examples section.
  • the invention also provides methods of alcohol steam reforming, reactors, and fuel processing systems that use these catalysts.
  • the invention provides a method of methanol steam reforming in which methanol and water vapor contact a catalyst; wherein the catalyst contains a palladium on zinc oxide catalyst and where at least 20% of the catalyst's pore volume is composed of pores in the size range of 0.1 to 300 microns. Neither powders nor pellets possess this type of porosity.
  • this reaction forms hydrogen from the reaction of said methanol and water vapor at a rate of at least 1.5 mole methanol per gram catalyst per hour (1.5 mole methanol / (g catalyst)(hr))
  • the invention provides a fuel processing system comp ⁇ sing a fuel tank connected to a reactor and a reactor connected (either directly or indirectly) to a fuel cell.
  • the reactor contains a palladium on zinc oxide catalyst where at least 20% of the catalyst's pore volume is composed of pores m the size range of 0.1 to 300 microns
  • the fuel cell is connected to the reactor such that hydrogen gas generated in the reactor can flow into the fuel cell either (1) directly or (2) indirectly with the use of down stream processing to either produce additional hydrogen in a water gas shift reactor and/or a secondary clean up process to reduce carbon monoxide levels or purify the hydrogen prior to ente ⁇ ng the fuel cell.
  • the invention provides a method of alcohol steam reforming in which methanol and water contact a catalyst, where the catalyst comprises palladium or ruthenium on cerium-promoted zircoma or alumina. Hydrogen is formed from the reaction of the methanol and water vapor over the catalyst.
  • the invention provides a catalyst that includes' a metal oxide support; a coating comp ⁇ sing zinc on the metal oxide support; and palladium in contact with the coating. This catalyst possesses a volumetric productivity of at least 10,000 ml H 2 / ml catalyst hr.
  • Preferred supports include: alumina ⁇ titania, and zircoma.
  • the weight % of the support in the catalyst is preferably 50 to 90%, preferably with 10 to 30 wt. % ZnO (measured based on elemental analysis for Zn, assuming all Zn is in the form of ZnO), and, preferably, 1 to 15 wt% Pd.
  • volumetric productivity is measured in a reactor with a 5 mm inner diameter, at 300 °C with premixed, vaporized water and methanol at a water to methanol ratio of 1.78, about 1 atm pressure and a contact time of 100 milliseconds (ms).
  • volumetric productivity is measured analogously except at a contact time (based on reactor volume) of 150 ms and where the engineered catalyst is sized to 5 cm x 0.94 cm x 0.3 mm (thickness is 0.3 mm) (or less, if unable to obtain this size) and placed in a channel having dimensions 2"x 0.37"x 0.05", 5 cm x 0.94 cm x 0.13 cm) that is located m (I e., a rectangular aperture machined in) the center of a stamless steel catalyst holder having a diameter of 1 3 cm.
  • two engineered catalysts were separated with a spacer and inserted into the channel. The spacer also holds catalysts against the walls of channel.
  • the catalyst has a productivity of at least 40,000, more preferably at least 60,000 and in some embodiments a productivity of 20,000 to 90,000.
  • the invention also includes a method of alcohol steam reforming comp ⁇ sing passing water and an alcohol in contact with the above-desc ⁇ bed catalyst.
  • the steam reforming reaction is earned out in a temperature range of 220 to 350, more preferably 250 to 320 °C.
  • the invention also includes alcohol-reforming catalyst systems in which the catalyst is present along with an alocohol and water, and, optionally, a reactor
  • the invention also provides a method of making a catalyst that includes the steps of. providing a solid metal oxide support; adding a solution comprising dissolved zinc to the solid metal oxide support; adding a base to increase pH; and subsequent to at least a portion of the step of adding a base, depositing Pd.
  • Preferred supports include: alumina, titania, and zircoma.
  • the metal oxide support could itself be deposited (either before or after the other steps) onto a large pore support This method is especially advantageous in aqueous solutions where the metal oxide support would normally have an acidic surface.
  • the dissolved Zn is at least partially, and more preferably completely, dissolved in a solvent.
  • the solution containing dissolved zinc contains at least zinc, but may also contain other components including metals; in some preferred embodiments there are no other metals in the zinc solution; in some prefe ⁇ ed embodiments the solution is 0.1 to 3 M zinc.
  • the order of addition, solid oxide to Zn solution or Zn solution to solid oxide is not critical and the inventive method includes either order.
  • the base can be added before, du ⁇ ng or after the zinc solution is added
  • the base is added after the zinc solution, more preferably it is added to slowly to result in gradual precipitation of zinc
  • the base is an aqueous ammonia solution
  • base is added until a pH of 7 or greater is obtained. Improvement is obtained where Pd is added after at least a portion of the base is added. Preferably, Pd is added after all the base has been added - this results in the greatest percentage of Pd being disposed on the catalyst surface.
  • Pd is preferably deposited on the catalyst after deposition of the zinc, and, in some prefe ⁇ ed embodiments, after the zinc-containing layer has been dried and, optionally, calcined. In some preferred embodiments, Pd is impregnated onto the Zn-contaimng support in solution, preferably aqueous solution.
  • the catalyst is prepared and reduced under hydrogen with temperatures never exceeding 400 °C. preferably, calcining of the Zn-containing catalyst, either before and/or after depositing Pd, is conducted at 200 to 400 C C, more preferably 250 to 350°C. Similar temperature ranges can be used when reducing (and operating) the catalyst.
  • the low temperature treatment increases catalyst life and surface area.
  • the invention also includes catalysts made by the foregoing methods.
  • Various embodiments of the invention can provide numerous advantages including one or more of the following: high conversions at relatively short contact times, selectivity control, and low temperature operation.
  • Fig 1 is a plot of methanol conversion vs. catalyst bed temperature for a powder and felt-supported Pd/ZnO catalyst.
  • Fig 2 is a plot of specific activity vs. temperature for a powder and felt-supported Pd/ZnO catalyst
  • Fig. 3 is a plot of pressure drop for the powder and felt-supported Pd/ZnO catalysts.
  • Fig. 4 is a schematic of a simplified fuel cell system that includes a cross-sectional view of a water gas shift reactor that includes a microchannel heat exchanger.
  • Fig. 5 is a schematic of catalyst testing apparatus.
  • Fig. 6 is a plot of methanol conversion vs. catalyst bed temperature for a va ⁇ ety of powder catalysts.
  • Fig. 7 is a plot of hydrogen selectivity vs catalyst bed temperature for a vanety of powder catalysts.
  • Fig. 8 is a plot of CO selectivity vs. catalyst bed temperature for a variety of powder catalysts.
  • the steam reforming catalyst requires catalytically active surface sites that reduce the kinetic barrier to the alcohol steam reforming reaction.
  • the active surface sites include palladium (Pd) and/or mthenium (Ru), Cu, and Pd-Zn alloy that are dispersed over the surface.
  • the catalyst preferably contains up to 30 wt% Pd, more preferably 2 to 10 wt%. In some embodiments, the catalyst preferably contains up to 10wt%, more preferably 0.2% to 5% weight percent Ru. Too little catalytically active metal, preferably Pd and/or Ru, can result in too few catalytic sites, while too much is costly due to lower dispersion.
  • the surface active sites are dispersed on a (preferably high surface area, BET surface area>10m 2 /g) metal oxide support.
  • Preferred metal oxides include ZnO, Zr0 2 , and A1 2 0 3 .
  • the metal oxide, including the presence of catalytically active surface sites, as measured by BET preferably has a volumetric average pore size of less than 0.1 micrometer ( ⁇ m).
  • the metal oxide, including the presence of catalytically active surface sites, as measured by BET, nitrogen physisorption preferably has a surface area of more than 10 m 2 /g, more preferably a surface area of 20 to 500 m 2 /g.
  • the metal oxide can be particles, preferably having diameters less than 4 mm, more preferably less than 1 mm, or, more preferably the metal oxide forms a layer (of agglomerated particles or a continuous film) having a thickness less than 4 mm, more preferably less than 1 mm, and still more preferably a thickness of less than 40 ⁇ m on large pore supports.
  • the catalyst may take any conventional form such as a powder or pellet.
  • the catalyst includes an underlying large pore support.
  • preferred large pore supports include commercially available metal foams and, more preferably, metal felts.
  • the large pore support has a porosity of at least 5%, more preferably 30 to 99%, and still more preferably 70 to 98%.
  • the support has a volumetric average pore size, as measured by BET, of 0.1 ⁇ m or greater, more preferably between 1 and 500 ⁇ m.
  • Preferred forms of porous supports are foams and felts and these are preferably made of a chemically and thermally stable and conductive material, preferably a metal such as stainless steel or FeCrAlY alloy.
  • porous supports are preferably thin, such as between 0.1 and 1 mm.
  • Foams are continuous structures with continuous walls defining pores throughout the structure.
  • Felts are fibers with interstitial spaces between fibers and includes tangled strands like steel wool.
  • Va ⁇ ous supports and support configurations are desc ⁇ bed in U.S. Patent Applications Ser. No. 09/640,903 (filed Aug. 16, 2000), which is incorporated by reference.
  • the catalyst with a large pore support (and including the spinel-supported catalyst) preferably has a pore volume of 5 to 98%, more preferably 30 to 95% of the total porous material's volume.
  • At least 20% (more preferably at least 50%) of the material's pore volume is composed of pores in the size (diameter) range of 0.1 to 300 microns, more preferably 0.3 to 200 microns, and still more preferably 1 to 100 microns.
  • Pore volume and pore size distribution are measured by mercury porisimetry (assuming cylindrical geometry of the pores) and nitrogen adsorption. As is known, mercury porisimetry and nitrogen adsorption are complementary techniques with mercury porisimetry being more accurate for measuring large pore sizes (larger than 30 nm) and nitrogen adsorption more accurate for small pores (less than 50 nm).
  • Pore sizes in the range of about 0.1 to 300 microns enable molecules to diffuse molecularly through the materials under most gas phase catalysis conditions.
  • the large-pore substrate has a corrugated shape that could be placed in a reaction chamber (preferably a small channel) of a steam reformer.
  • catalyst with the aforementioned preferred compositions can be prepared by a co- precipitation method using inorganic or organometallic precursors.
  • the powder can be slurry coated over the substrate at any stage in the preparative process.
  • a high surface area metal oxide could be slurry coated onto the substrate followed by depositing, drying and activating a metal via the impregnation method.
  • a vapor coat or soluble form of alumina could be applied onto the substrate.
  • solution or slurry coating is typically less expensive, vapor coating of the various materials could also be employed.
  • the present invention also provides methods of steam reforming in which an alcohol is reacted with water vapor at short contact times over the catalysts described above.
  • the contact time is preferably less than 1 s, more preferably 10-500 milliseconds (msec).
  • the alcohol steam reforming reaction is preferably carried out at 200-500 °C, more preferably 240-400 °C.
  • the reaction can be run over a broad pressure range from sub-ambient to very high.
  • the alcohol is a C
  • Certain aspects of the invention can best be desc ⁇ bed in terms of properties such as conversion, selectivities, specific activity, and pressure drop.
  • the catalyst when tested at short contact times in the apparatus schematically illustrated m Fig. 5, or equivalent apparatus, shows good alcohol conversions, selectivities, specific activity and low pressure drop.
  • Alcohol conversion is preferably at least 50%, more preferably at least 80% and still more preferably at least 90%.
  • Hydrogen selectivity defined as moles H atoms in H 2 in the product gas divided by moles H in all product gases, is preferably at least 50%, more preferably at least 60%, still more preferably at least 85%.
  • Preferred embodiments of the inventive catalysts and methods may also be desc ⁇ bed in te ⁇ ns of their exceptionally high specific activity.
  • the catalyst and/or method has a specific activity of greater than 1 5 mol methanol converted/(g catalyst)(hr) when tested at 400C, 25 msec contact time, 1.8 steam-to-carbon ratio; and the catalyst exhibiting this specific activity preferably has a pressure drop of less than 25 psig.
  • One embodiment of a reactor 2 is shown m cross-section in Fig. 4. The reaction chamber
  • a microchannel heat exchanger 12 can be placed m contact with the reaction chamber.
  • the microchannel heat exchanger 12 has channels 14 for passage of a heat exchange fluid These channels 14 have at least one dimension that is less than 1 mm. The distance from the channels 14 to catalyst 6 is preferably minimized in order to reduce the heat transport distance.
  • MicroChannel heat exchangers can be made by using known techniques which include such methods as electrodischarge machining (EDM), wire EDM, conventional machming, and the like.
  • EDM electrodischarge machining
  • wire EDM wire EDM
  • conventional machming and the like.
  • An example of example fabrication methods is described in Tonkovich et al., 1997, Proceedings of the 2 nd International Conference on Microreaction Technology, p. 45-53.
  • the preferred reaction chamber for the steam reforming reaction may be of any length or height.
  • the preferred reaction chamber width is less than 2 mm. More preferably the reaction chamber width is less than 1 mm.
  • the reaction chamber is preferably in thermal contact with a heat exchange chamber.
  • the heat exchange chamber in thermal contact with the reaction chamber may also be of any length or height. Preferably the length and height of the heat exchange chamber is close to the dimensions of the reaction chamber.
  • the heat exchange chamber is adjacent to the reaction chamber in an interleaved chamber onentation (width is the direction m which the interleaved reaction chambers and heat exchangers stack).
  • the width of the heat exchanger chamber is preferably less than 2 mm. More preferably the width of the heat exchange chamber is less than 1 mm.
  • the direction of flow in the heat exchange chamber may be either co-current, counter-current, or cross-flow. This approach will enable excellent heat transfer performance.
  • the alcohol reforming reactor may also be configured by placing the reaction chamber adjacent to a heat exchanger chamber that is comprised of an array of microchannels rather than a single microchannel
  • the width of the reaction chamber may exceed 2 mm, but at least one dimension of a single microchannel in the array must be less than 2mm. Preferably this dimension is less than 1 mm
  • the allowable width of the reaction chamber is a strong function of the effective thermal conductivity of the catalyst insert. The higher the effective thermal conductivity, the wider the insert to enable rapid heat removal. For effective thermal conductivites on the order of 2 W/m K, it is anticipated that the maximum reaction chamber width must remain less than 2 mm and preferably 1 mm.
  • the reaction chamber 4 is connected to fuel tank 16 such that alcohol from the tank can flow into the reaction chamber.
  • fuel tank 16 a fuel tank is shown in the Figure, it should be recognized that any alcohol fuel source, such as a pipeline could be used
  • the liquid fuel stream may flow through a separate vaporizer or be vapo ⁇ zed within a section of the steam-reforming reactor.
  • the alcohol is vaporized in a microchannel vaporizer and/or preheated in a microchannel preheater.
  • the product gases may either flow into fuel cell 22 where the H 2 is combined with 0 2 to generate electricity, or the product of the methanol reforming reactor may flow into a water gas shift reactor to convert some of the carbon monoxide into carbon dioxide and additional hydrogen.
  • This stream may flow directly into a fuel cell 22, or may flow into a secondary clean up process to further purify hydrogen or reduce carbon monoxide to a level that can be accommodated in a fuel cell
  • the secondary clean-up process may include a preferential oxidation reactor, membrane separation of either hydrogen or carbon monoxide, a sorption based separation system for either hydrogen or carbon monoxide, and the like.
  • heat from a combustor will be used to generate heat for other processes such as generating steam (not shown) that can be utilized for steam reformer and/or water gas shift reactor.
  • generating steam (not shown) that can be utilized for steam reformer and/or water gas shift reactor.
  • fuel cell 22 Various fuel cells are well-known and commercially available and need not be described here Instead of fuel cell 22, the hydrogen-containing gas could go to: a storage tank, a refueling station, a hydrocracker, hydrotreater, or to additional hydrogen punfiers.
  • EXAMPLES The following examples are generalized descriptions based on typical conditions used to make numerous samples. Certain temperature ranges, etc. set forth prefe ⁇ ed ranges for conducting various steps
  • the incipient wetness technique was employed to deposit Ru metal onto the alumina support Initially, an alumina support was treated by oxidatively calcining gamma alumina at a temperature of about 350 to 550 °C to remove water from the micropores of the support
  • aqueous Ru solution was prepared by diluting Ru(III)n ⁇ trosyl (obtained from Ald ⁇ ch Chemical Co as an aqueous solution of dilute nitric acid containing 1.5 wt% Ru) with DI water.
  • non-aqueous Ru solution could be used by dissolving an organic Ru compound in an organic solvent such as acetone.
  • the target Ru concentration in the fired catalyst was 1-3 wt%.
  • the amount of Ru solution utilized was an amount that is at least equivalent to the pore volume of the alumina utilized.
  • the impregnated catalyst was d ⁇ ed at a temperature of 100°C for a pe ⁇ od of 12 hours m air so as to spread the metal over the entire support.
  • the d ⁇ ed catalyst was calcined by heating slowly in air at rate of 2°C/m ⁇ n, to a temperature in the range of 300 to 500°C, that is sufficient to decompose the metal salts.
  • the aforesaid drying and calcinations steps can be done separately or can be combmed
  • Cerium oxide was impregnated on Zr0 2 using Ce(N0 3 ) 3 hexahydrate from Ald ⁇ ch. The desired concentration of Ce was from 1 to 3 wt%. After impregnation, the Ce promoted Zr0 2 was dried and calcined according to the procedure desc ⁇ bed in above examples. Pd and Ru were co-impregnated on CeO-Zr0 Pd(N0 3 ) 2 solution contammg 20wt% Pd (Engelhard) was mixed with 1 5 wt%Ru(III)n ⁇ trosyl (Ald ⁇ ch) at a pre-determined ratio. The amount of Pd-Ru solution utilized was an amount at least equivalent to the pore volume of the CeO-Zr0 2 utilized.
  • sequential impregnation may be used by repeatedly adding Pd-Ru solution Between each impregnation step, catalyst was dried and calcined After the last impregnation and calcinations sequence, the metal impregnated catalyst support was subjected to an activation treatment, preferably reduction at 300-500°C.
  • an activation treatment preferably reduction at 300-500°C.
  • Pd/ZnO catalyst is prepared by impregnating Pd(N0 3 ) 2 solution (Engelhard, 20 wt% Pd) on ZnO oxide (Ald ⁇ ch). Typical Pd loading varied from 5 to 20 wt%. The impregnation procedure was similar to that used in the above examples. After impregnation, the catalyst was calcined at 350-550 °C.
  • Pd-ZnO can be coated on a high surface area support such as A1 2 0 3 . Coating Pd-Zn on A1 2 0 3 enhances available surface area so as to increase the number of active sites.
  • a thin layer of ZnO is formed on A1 2 0 3 surface This can be done by soaking 2 0 gram of A1 2 0 3 in 0 5M Zn(N0 3 ) 2 solution, followed by drying at 100°C and calcining at 350 °C.
  • Pd is introduced by impregnating ZnO- A1 2 0 3 with Pd(N0 3 ) 2
  • the amount of Pd(N0 3 ) 2 used depends on the desired loading of Pd which varies from 5 to 20 wt %
  • the catalyst was subjected to final calcinations in air at 350-650°C. P ⁇ or to steam reforming reaction, the catalyst should be reduced by hydrogen at 125-500°C.
  • Pd nitrate and Zn nitrate can be co-impregnated on alumina.
  • a Pd and Zn nitrate solution is prepared at a pre-determined ratio, the solution that contains both Pd and Zn can be impregnated on A1 2 0 3 .
  • Example 4 Engineered steam reforming catalyst Catalyst was coated on FeCrAlY felt (obtained from Technetics, Deland, FL) using a wash-coating technique
  • Catalyst in the powder form was prepared using methods described in examples 1-3.
  • Catalyst coating slurry was prepared by mixing powder catalyst with de-ionized water in the ratio of 1 6 The mixture was ball-milled for 24 hours to obtain coating slurry contammg catalyst particles less than 1 micron Before wash coating, metal felt is pretreated by a rapid heating to 900°C in air for 2 hours The heat-treated felt was wash-coated by dipping the felt into catalyst slurry. The wash coating process may be repeated to obtain desired weight gain.
  • the felt coated with catalyst was d ⁇ ed in an oven at 100°C for 1 hour. The coating procedure is repeated to achieve desired coating thickness.
  • the catalyst was dried overnight in an oven at 100°C and calcined by heating slowly in air at rate of 2°C/m ⁇ n to a temperature in the range of 300 to 500°C. The amount of catalyst coated was measured to be 0.1 gram catalyst per square inch (6.5 cm 2 ) of felt. After coating, the felt coated with catalyst was calcined at between 300-500°C for 3 hours in air.
  • the engineered catalyst felt was subjected to an activation treatment, preferably reduction at 300-400°C. The above procedure can be applied to metal foams made of stainless steel, copper, alloys, etc.
  • Two engineered catalysts (2"x 0.35"x 0.01", 5 cm x 0.89 cm x 0.03 cm) were inserted within the single channel device and in contact with channel with a gap of 0.0254 cm in between.
  • the single channel device was placed in a tube furnace. Reactants were preheated in the top zone of the furnace, and were introduced into the single channel device in a down-flow mode.
  • Steam reforming of methanol was conducted at a fixed contact time, a steam-to-carbon ratio of 1.8/1, and a temperature maintained at 250 to 500 °C (chamber temperature was continuously monitored by a thermocouple). Effluent flowrate was measured by a bubble flowmeter, and product was analyzed using gas chromatography.
  • the performances of Pd/ZnO or other methanol steam refo ⁇ mng catalysts can be further improved by optimizing the mass and heat transfer characte ⁇ stics of the engineered ("engineered” refers to catalysts having a large pore support) catalysts.
  • Alumma (BET surface area 220 m 2 /g, Engelhard Corp.) was heated at 5 °C per mmute to 500 °C and maintamed for 2 hours
  • One gram of the calcined alumina was added to 69 ml of IM zinc nitrate solution at room temperature.
  • the resulting slurry was stirred at room temperature on a stir ⁇ ng plate.
  • Ammonium hydroxide was added dropwise mto the slurry while the pH of the solution was monitored. This allows Zn to precipitate onto the alumina (presumably as a hydroxide). Ammonium hydroxide was added until the solution reached pH 8.
  • the slurry was then stirred 1.5 hours
  • the solids were filtered off, washed with deionized water and d ⁇ ed in a vacuum oven at 110 °C overnight, then heated in air at 2 °C per minute to 350 °C and maintained for 6 hours.
  • the desired level of Pd was added from a 20 wt% Pd(N0 3 ) 2 solution (obtamed from Engelhard Corp.) by the incipient wetness impregnation technique.
  • the solids were filtered off, washed with deionized water and d ⁇ ed m a vacuum oven at 110 °C overnight, then heated in air at 2 °C per minute to 350 °C and maintained for 6 hours.
  • the catalyst powder desc ⁇ bed above was combined with deionized water (m a water to catalyst weight ratio of at least 7) and comminuted with alumina grinding balls on a rotating device for at least one day.
  • a FeCrAlY felt was cut and trimmed to size and pretreated by heating at 20 °C per minute to 900 °C and maintained for 2 hours to fonn a surface alumina layer
  • the resulting felt was dipped into the comminuted slurry then dried in vacuum at 1 10 °C for 20 minutes and repeating until reaching a target weight gam of 0.1 g per square inch (0.015 g per cm 2 ) of (2"x 0 37"x 0.01", 5 cm x 0.94 cm x 0.3 mm - thickness is 0.3 mm) felt.
  • the catalyst was d ⁇ ed 8 hours, then heated in air at 2 °C per minute to 350 °C and maintained for 6 hours.
  • the catalysts of Example 5 were tested m
  • the reactor used for powder testing had an inner diameter of 5 mm.
  • Typical catalyst loadmg was 0.06 g of 70-100 mesh powder.
  • two catalysts were separated by a spacer and were placed m a channel having dimensions 2"x 0.37"x 0.05", 5 cm x 0.94 cm x 0.13 cm) that is located in (i.e., a rectangular aperture machmed in) the center of a stainless steel catalyst holder (diameter 0.5 inch, 1.3 cm).
  • the spacer held the catalyst against the walls of the channel.
  • Steam reforming was conducted at between 220-475 °C and room pressure. Prior to testing, the catalysts were reduced in a 10 hydrogen stream at a temperature of 125 to 350 °C.
  • a mixture of N 2 and H 2 were fed during startup to establish steady state flow and to heat the reactor to the operating temperature When the catalyst bed reached the target temperature, premixed water and methanol at a ratio of 1 78 were vaporized in a preheater and fed into the reactor.
  • Hydrogen flow was discontinued while nitrogen flow continued to stabilize flow Feed rate is set to give desired contact time.
  • desired contact time is 100 msec
  • total flow rate should be set at 363 ml/min
  • the reaction products were analyzed by on-line gas chromatography. Methanol conversion is calculated based on feed and product flow rates and carbon balance.
  • a catalyst composed of about 70 wt% alumina, about 20 wt% zinc oxide, and 10 wt% Pd was tested as a powder and on a felt. The powder was tested at 1 atmosphere, 280 °C, a contact time of 100 msec and a LHSV of 30.5 h ', and achieved a productivity of 29,000 ml H 2 / ml catalyst hr.
  • the engineered catalyst was tested at 1 atmosphere, 300 °C, a contact time of 150 msec and a LHSV of 130 h "1 , and achieved a productivity of 90,000 ml H 2 / ml catalyst hr (based on catalyst volume, not reaction chamber volume).
  • powder catalysts having 1, 5, 10 and 15 wt% Pd were tested at 1 atmosphere, 294 °C, a contact time of 100 msec and a LHSV of 28 h "1 ; these catalysts were found to have productivities of 13,300, 19,400, 19,500 and 20,600 ml H 2 / ml catalyst hr, respectively. Indicating that at 5 wt% Pd and above, Pd loading levels have very little impact on productivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne des catalyseurs, des réacteurs et des procédés de reformage à la vapeur d'alcools sur un catalyseur. Les propriétés et les résultats surprenants obtenus par les procédés et les catalyseurs selon l'invention sont également décrits.
PCT/US2002/004527 2001-02-16 2002-02-15 Catalyseurs de reformage et procedes de reformage d'alcools a la vapeur WO2002066370A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/788,294 US6936237B2 (en) 1999-08-17 2001-02-16 Reforming catalysts and methods of alcohol steam reforming
US09/788,294 2001-02-16
US10/076,881 US7335346B2 (en) 1999-08-17 2002-02-13 Catalyst and method of steam reforming

Publications (2)

Publication Number Publication Date
WO2002066370A2 true WO2002066370A2 (fr) 2002-08-29
WO2002066370A3 WO2002066370A3 (fr) 2003-04-03

Family

ID=26758573

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/004527 WO2002066370A2 (fr) 2001-02-16 2002-02-15 Catalyseurs de reformage et procedes de reformage d'alcools a la vapeur

Country Status (2)

Country Link
AU (1) AU2002242176A1 (fr)
WO (1) WO2002066370A2 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005030390A1 (fr) * 2003-05-07 2005-04-07 Battelle Memorial Institute Catalyseurs de reformage d'alcools a la vapeur et procedes de reformage d'alcools a la vapeur
EP1684373A2 (fr) * 2005-01-05 2006-07-26 Samsung SDI Co., Ltd. Substrat de réaction pour réformeur de pile à combustible, méthode de fabrication du substrat et réformeur incluant le substrat
EP1745846A2 (fr) * 2005-07-20 2007-01-24 Fuji Photo Film Co., Ltd. Catalyseur métallique, procédé de sa préparation et Microréacteur avec un tel catalyseur
WO2007029872A2 (fr) * 2005-09-08 2007-03-15 Casio Computer Co., Ltd. Reacteur et appareil electronique
US7208136B2 (en) 2003-05-16 2007-04-24 Battelle Memorial Institute Alcohol steam reforming catalysts and methods of alcohol steam reforming
US7514513B2 (en) 2005-08-12 2009-04-07 Fujifilm Corporation Polymer, film-forming composition comprising the polymer, insulating film formed by using the composition and electronic device
EP2216093A1 (fr) * 2009-01-30 2010-08-11 Corning Incorporated Formation et dépôt in situ de palladium Pd(0) dans des réacteurs
CN114984864A (zh) * 2022-05-05 2022-09-02 华东理工大学 一种高能效低碳排放内部电加热固定床制氢反应器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6082137A (ja) * 1983-10-14 1985-05-10 Mitsubishi Heavy Ind Ltd メタノ−ル改質用触媒
EP0278749A1 (fr) * 1987-02-12 1988-08-17 Ngk Insulators, Ltd. Corps de cordiérite en structure en nid d'abeilles et méthode pour le produire
EP1063011A1 (fr) * 1999-05-22 2000-12-27 Degussa-Hüls Aktiengesellschaft Catalyseur pour le réformage à la vapeur des alcools

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6082137A (ja) * 1983-10-14 1985-05-10 Mitsubishi Heavy Ind Ltd メタノ−ル改質用触媒
EP0278749A1 (fr) * 1987-02-12 1988-08-17 Ngk Insulators, Ltd. Corps de cordiérite en structure en nid d'abeilles et méthode pour le produire
EP1063011A1 (fr) * 1999-05-22 2000-12-27 Degussa-Hüls Aktiengesellschaft Catalyseur pour le réformage à la vapeur des alcools

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CUBEIRO M L ET AL: "Partial oxidation of methanol over supported palladium catalysts" APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 168, no. 2, 27 March 1998 (1998-03-27), pages 307-322, XP004271359 ISSN: 0926-860X *
IWASA N ET AL: "STEAM REFORMING OF METHANOL OVER PD/ZNO: EFFECT OF THE FORMATION OF PDZN ALLOYS UPON THE REACTION" APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 125, no. 1, 1995, pages 145-157, XP000562506 ISSN: 0926-860X cited in the application *
PATENT ABSTRACTS OF JAPAN vol. 009, no. 218 (C-301), 5 September 1985 (1985-09-05) & JP 60 082137 A (MITSUBISHI JUKOGYO KK), 10 May 1985 (1985-05-10) *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005030390A1 (fr) * 2003-05-07 2005-04-07 Battelle Memorial Institute Catalyseurs de reformage d'alcools a la vapeur et procedes de reformage d'alcools a la vapeur
US7208136B2 (en) 2003-05-16 2007-04-24 Battelle Memorial Institute Alcohol steam reforming catalysts and methods of alcohol steam reforming
EP1684373A2 (fr) * 2005-01-05 2006-07-26 Samsung SDI Co., Ltd. Substrat de réaction pour réformeur de pile à combustible, méthode de fabrication du substrat et réformeur incluant le substrat
EP1684373A3 (fr) * 2005-01-05 2006-10-04 Samsung SDI Co., Ltd. Substrat de réaction pour réformeur de pile à combustible, méthode de fabrication du substrat et réformeur incluant le substrat
US7935315B2 (en) 2005-01-05 2011-05-03 Samsung Sdi Co., Ltd. Reformer for a fuel cell system, reaction substrate therefor, and manufacturing method for a reaction substrate
CN100423344C (zh) * 2005-01-05 2008-10-01 三星Sdi株式会社 燃料电池系统的重整器、反应基板及反应基板的制造方法
EP1745846A3 (fr) * 2005-07-20 2007-08-22 FUJIFILM Corporation Catalyseur métallique, procédé de sa préparation et Microréacteur avec un tel catalyseur
EP1745846A2 (fr) * 2005-07-20 2007-01-24 Fuji Photo Film Co., Ltd. Catalyseur métallique, procédé de sa préparation et Microréacteur avec un tel catalyseur
US7514513B2 (en) 2005-08-12 2009-04-07 Fujifilm Corporation Polymer, film-forming composition comprising the polymer, insulating film formed by using the composition and electronic device
WO2007029872A3 (fr) * 2005-09-08 2007-11-15 Casio Computer Co Ltd Reacteur et appareil electronique
WO2007029872A2 (fr) * 2005-09-08 2007-03-15 Casio Computer Co., Ltd. Reacteur et appareil electronique
US7713317B2 (en) 2005-09-08 2010-05-11 Casio Computer Co., Ltd. Reformer for power supply of a portable electronic device
EP2216093A1 (fr) * 2009-01-30 2010-08-11 Corning Incorporated Formation et dépôt in situ de palladium Pd(0) dans des réacteurs
CN114984864A (zh) * 2022-05-05 2022-09-02 华东理工大学 一种高能效低碳排放内部电加热固定床制氢反应器
CN114984864B (zh) * 2022-05-05 2023-09-01 华东理工大学 一种高能效低碳排放内部电加热固定床制氢反应器

Also Published As

Publication number Publication date
AU2002242176A1 (en) 2002-09-04
WO2002066370A3 (fr) 2003-04-03

Similar Documents

Publication Publication Date Title
US6936237B2 (en) Reforming catalysts and methods of alcohol steam reforming
US20090297434A1 (en) Reforming Catalysts and Methods of Alcohol Steam Reforming
US7776113B2 (en) Catalysts, reactors and methods of producing hydrogen via the water-gas shift reaction
EP2251080B1 (fr) Corps catalytique poreux qui décompose les hydrocarbures et son procédé de fabrication, procédé de préparation d'un gaz reformé mixte qui comprend de l'hydrogène à partir d'un hydrocarbure et système de piles à combustible
JP5691098B2 (ja) 一酸化炭素の選択的メタン化触媒、その製造方法及びそれを用いた装置
EP1251949B1 (fr) Procede et appareil permettant d'obtenir une vitesse de production amelioree de reactions chimiques thermiques
US6562315B2 (en) Suppression of methanation activity by a water gas shift reaction catalyst
EP1537046B1 (fr) Article simplifie destine a l'evacuation du monoxyde de carbone
EP2539069B1 (fr) Catalyseurs à base de particules nanométriques d'or pour oxydation du monoxyde de carbone et réactions de déplacement gaz-eau
Abbasi et al. Synthesis and physicochemical characterization of nanostructured Pt/CeO2 catalyst used for total oxidation of toluene
US20020147103A1 (en) Enhanced stability water-gas shift reaction catalysts
EP1759764A1 (fr) Catalysateur contenant de l'alumine, du cerium et au moins 10% (exprimé en poids d'oxyde) de Strontium ou/et Barium pour le traitement des gaz d'échappement contenant des NOx.
US6790432B2 (en) Suppression of methanation activity of platinum group metal water-gas shift catalysts
Qihai et al. Hydrogen production by steam reforming of ethanol over copper doped Ni/CeO2 catalysts
Patel et al. Influence of preparation method on performance of Cu (Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol
KR101365787B1 (ko) Ｐｔ－Ｒｅ 바이메탈 수성 가스 전환 촉매를 위한 공정조건
MX2008006912A (en) Process conditions for pt-re bimetallic water gas shift catalysts
WO2002066370A2 (fr) Catalyseurs de reformage et procedes de reformage d'alcools a la vapeur
Ates et al. Thin‐Film Catalytic Coating of a Microreactor for Preferential CO Oxidation over Pt Catalysts
JP4328627B2 (ja) ルテニウムと酸化亜鉛を含有する共酸化触媒
WO2007075432A2 (fr) Procedes de production d'hydrogene par reaction de deplacement eau-gaz sur un catalyseur pd-zn
Mileva et al. NANOSIZED MESOPOROUS CuO-CeO 2-TiO 2 AND CuO-ZrO 2-TiO 2 COMPOSITES AS CATALYSTS FOR METHANOL DECOMPOSITION: EFFECT OF MODIFICATION PROCEDURE.
Mahmud et al. Amorphous structure in Cu-Zn-V-Al oxide composite catalyst for methanol reforming
WO2006065138A1 (fr) Catalyseur de particules d’or sur support mixte pour l’oxydation selective de co en presence de h2
Ravuru Glycerol Steam Reforming to Produce Hydrogen Using Magnesium on Alumina and Other Supports

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载