+

WO2009058569A2 - Catalyst for reforming hydrocarbons - Google Patents

Catalyst for reforming hydrocarbons Download PDF

Info

Publication number
WO2009058569A2
WO2009058569A2 PCT/US2008/080069 US2008080069W WO2009058569A2 WO 2009058569 A2 WO2009058569 A2 WO 2009058569A2 US 2008080069 W US2008080069 W US 2008080069W WO 2009058569 A2 WO2009058569 A2 WO 2009058569A2
Authority
WO
WIPO (PCT)
Prior art keywords
surface area
catalyst
area material
rhodium
high surface
Prior art date
Application number
PCT/US2008/080069
Other languages
French (fr)
Other versions
WO2009058569A3 (en
Inventor
Jon P. Wagner
Chandra Ratnasamy
Charles D. Faulk
Original Assignee
Sud-Chemie Inc.
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 US11/931,391 external-priority patent/US20090108238A1/en
Priority claimed from US11/933,535 external-priority patent/US20090118119A1/en
Application filed by Sud-Chemie Inc. filed Critical Sud-Chemie Inc.
Publication of WO2009058569A2 publication Critical patent/WO2009058569A2/en
Publication of WO2009058569A3 publication Critical patent/WO2009058569A3/en

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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • 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
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • C01B2203/0205—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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/10—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
    • C01B2203/1064—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
    • C01B2203/12—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
    • 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

  • An embodiment of the present invention relates to catalysts for catalytic reforming of hydrocarbons utilizing a precious metal deposited upon a support, wherein the support is formed from a mixture of a low surface area material and a high surface area material.
  • An embodiment of the present invention also relates to processes for the preparation of the reforming catalyst and processes for use of the reforming catalysts for reforming hydrocarbons.
  • the autothermal reaction converts all fuel to CO 2 and H 2 .
  • the reaction is conducted near thermal neutral conditions.
  • the autothermal reaction has shown particular utility as a process for use with fuel cells as autothermal reforming can be an effective method for generating hydrogen from hydrocarbon fuels while producing conventional reaction by products.
  • the hydrocarbon fuel stream can be derived from a number of conventional fuel sources, with the preferred fuel sources including natural gas, propane and LPG.
  • a conventional hydrogen generation system particularly a fuel cell processing train
  • the hydrocarbon fuel stream is passed over and/or through a desulfurization system to be desulfurized.
  • the desulfurized hydrocarbon fuel stream then flows into a reformer, wherein the fuel stream is converted into a hydrogen-rich fuel stream.
  • the reformer may utilize any conventional reforming reaction such as steam reforming, partial oxidation or autothermal reforming.
  • the fuel stream passes through one or more heat exchangers to a shift converter where the amount of CO in the fuel stream is reduced. From the shift converter the fuel stream again passes through various heat exchangers and then through a selective oxidizer or selective methanizer having one or more catalyst beds, after which the hydrogen rich fuel stream flows to the fuel cell stack where it is utilized to generate electricity.
  • a number of reforming catalysts are known, improved reforming catalysts are needed which exhibit a high percentage of conversion of the feed stream into hydrogen, while retaining stability at high temperatures.
  • One object of a preferred embodiment of the invention is to produce reforming catalysts which exhibit high conversion capacity while retaining significant surface area stability, even at high temperatures.
  • Another object of a preferred embodiment of the invention is a process for the production of the reforming catalysts .
  • Another object of a preferred embodiment of the invention is a use of these catalysts for reforming conventional feed streams.
  • Figure 1 is a graph illustrating the CH 4 conversion percentage over time for three catalysts operating at the stated conditions. The composition of the catalysts is described in the Examples.
  • Figure 2 is a graph illustrating the retention of surface area at high calcination temperatures for the three catalysts of Figure 1.
  • One of the preferred embodiments of the invention disclosed herewith is a catalyst for reforming hydrocarbons comprising one or more precious metals, selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium, and combinations thereof, with the combination of rhodium and platinum preferred, deposited on a support, wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m 2 /g, preferably from 1 m 2 /g to 10 m 2 /g, and from 40 to 90 percent of a high surface area material, wherein the surface area of the high surface area material is from 80 m 2 /g to 300 m 2 /g, preferably from 80 m 2 /g to 200 m 2 /g.
  • the catalyst composition may be formed as a tablet, extrudate or powder or washcoated on a cordierite or
  • Another embodiment is various processes for reforming a hydrocarbon feed stream utilizing the catalysts described above utilizing steam reforming, partial oxidation or autothermal reforming processes.
  • a further embodiment is a process of forming the catalysts described above.
  • One embodiment of the present invention is a catalyst tablet or extrudate or catalytic washcoat for reforming hydrocarbons comprising one or more precious metals, selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium, and combinations thereof, deposited upon a support, wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m 2 /g, and from 40 to 90 percent of a high surface area material, wherein the surface area of the high surface area material is from 80 to 300 m 2 /g.
  • the catalyst or catalytic washcoat can be utilized for a number of reforming reactions including steam reforming, catalytic partial oxidation and autothermal reforming reactions.
  • the catalyst or catalytic washcoat for reforming hydrocarbons comprises one or more precious metals deposited upon a support.
  • the one or more precious metals that are deposited upon the support are selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium and combinations thereof.
  • the precious metal utilized comprises rhodium utilized alone.
  • rhodium and platinum are utilized together.
  • the total quantity of the precious metal (s) that is deposited upon the support for the reforming catalyst or catalytic washcoat of one embodiment of the invention is from 0.05 to 5 percent by weight, preferably from 0.1 to 3 percent by weight.
  • the catalyst comprises from 0.1 to 5 percent of rhodium.
  • the precious metal comprises a combination of from 0.1 percent to 2 percent of rhodium and from 0.05 to 3 percent of platinum.
  • a reforming catalyst with improved performance characteristics, especially high temperature stability can be produced when the support for the precious metal is formed from a mixture comprising a low surface area material and a high surface area material. While a person skilled in the art would have anticipated that the mixture of a high surface area material and a low surface material would yield a material with a surface area in between the surface areas of the two materials, it has surprisingly been discovered that the combination yields a material with a higher than expected surface area retention at high temperatures with greater stability for the desired reactions.
  • low surface area means less than 20 m 2 /g and preferably from 1 m 2 /g to 10 m 2 /g.
  • One embodiment of the low surface area material of the invention includes a calcium compound combined with an aluminum compound or a MeO/alumina compound, wherein Me is selected from Ca, Sr, Ba, Mg, Mn, Ni and combinations thereof.
  • Preferred low surface area materials include various aluminates, more preferably calcium aluminate, various hexaaluminates, more preferably selected from barium hexaaluminate, strontium hexaaluminate, manganese hexaaluminate, magnesium hexaaluminate, and combinations thereof.
  • the low surface area material is a mixture of calcium aluminate and a hexaaluminate, most preferably barium hexaaluminate.
  • the low surface area material mixture comprises substantially all a hexaaluminate or mixture of hexaaluminates.
  • CaO- 6Al 2 O 3 CaO -2Al 2 O 3 and CaO-Al 2 O 3 .
  • any stable calcium aluminate can be utilized.
  • the preferred low surface area material can be produced by conventional procedures, such as by physically mixing the calcium compound or the MeO with the alumina compound and then calcining the resultant mixture, or by purchasing the low surface area material, for example, by purchasing a S ⁇ d- Chemie G90 support material.
  • a "high surface area" material has a surface area from 80 to 300 m 2 /g, preferably from 80 to 200 m 2 /g.
  • One preferred embodiment of the high surface material comprises a high surface area alumina onto which has been impregnated various dopants, including one or more selected from the group consisting of yttria, ceria, zirconia and oxides of the lanthanides.
  • the preferred alumina is a transitional alumina, preferably gamma alumina, with a surface area greater than 200 m 2 /g, preferably up to 250 m 2 /g or so.
  • a particularly preferred embodiment of the high surface area material comprises a gamma alumina onto which has been impregnated ceria, yttria, and lanthana .
  • a most preferred high surface area material comprises 1 - 5% yttria, 1 - 5% lanthana, 14 - 20% ceria with the remaining amount comprising gamma alumina, with all amounts determined by weight.
  • Additional dopants can be added to this high surface area ceria, yttria and lanthana on alumina material including zirconia.
  • Other dopants which may also be added include Sn, Mn, Pr, Nd, Nb, Sm, W, their oxides and mixtures thereof.
  • Another preferred high surface area material is a mixed metal oxide material with oxides selected from two or more of the following: zirconia, ceria, titania, silica, lanthana, praseodymia, neodymia, yttria, samaria, tungsten oxide, molybdenum oxide, calcium oxide, chromium oxide, manganese oxide and magnesium oxide.
  • One particularly preferred high surface area mixed metal oxide combination comprises zirconia and ceria, with the preferred ratio of zirconia to ceria being 1 to 10 to 10 to 1.
  • praseodymia and/or neodymia are added to the ceria/zirconia support.
  • the praseodymia and/or neodymia preferably comprise from 3% to 30% of the support, by weight. When both are present in the support, the ratio of the praseodymia to the neodymia is preferably from 1 to 1 to 3 to 1.
  • the mixed metal oxide support high surface area material can be produced by blending together the metal oxides using conventional procedure or the mixed metal oxide can be purchased from conventional sources separately or after combination thereof.
  • the high surface area material may preferably comprise high surface area ceria, titania, or silica and mixtures thereof.
  • the low surface area material and the high surface area material are combined to produce the carrier for the reformer catalyst of one embodiment of the invention.
  • Various conventional production procedures may be used for this combination.
  • the high surface area material and the low surface area material are physically mixed, calcined and then washcoated onto a surface by conventional washcoat procedures or extruded to form extrudates.
  • the composition after mixing and calcining, can be formed into powders or tablets.
  • the precious metal material is impregnated onto that support.
  • the precious metal is incorporated into the support material, preferably by impregnation, in the form of a precious metal salt solution.
  • the support material when the precious metal is rhodium, the support material may be immersed in a rhodium salt solution, such as rhodium nitrate, and then dried and calcined at a temperature from 350° to 650 0 C for 1 to 5 hours to transform the rhodium salt to rhodium oxide.
  • a rhodium salt solution such as rhodium nitrate
  • multiple impregnation steps may be needed.
  • the surface area of the catalyst is preferably from 100 m 2 /g to 200 m 2 /g, more preferably from 100 m 2 /g to 170 m 2 /g, and most preferably from 150 m 2 /g to 160 m 2 /g.
  • the catalysts of the preferred embodiments are especially useful for reforming reactions, including steam reforming, partial oxidation and autothermal reforming, where the feed stream contains hydrocarbons, such as CH 4 .
  • a quantity of steam may be added to the feed stream along with a source for oxygen.
  • the reforming conditions include a molar steam/carbon ratio of 0.1 to 10, preferably 0.5 to 5 at a temperature from 350 0 C to 900 0 C, preferably 450 0 C to 800 0 C.
  • the feed stream passes over or through a bed containing the invention catalyst in the form of extrudates, tablets or powders.
  • the feed stream may pass over a support onto which the catalytic material of the invention has been deposited.
  • Catalyst A The catalyst of a preferred embodiment of the invention (Catalyst A) is compared by performance with a catalyst containing the same precious metal loading but deposited solely on a high surface area material (Catalyst B) and also a catalyst with the same precious metal loading deposited on a low surface area material (Catalyst C) .
  • Catalyst A is produced by depositing 0.8 percent rhodium on a carrier produced from a mixture of a low surface area material and a high surface area material.
  • the low surface area material comprises calcium hexaaluminate, wherein 13% comprises calcium with the remaining amount being alumina, and the high surface area material comprises 1.5 % by weight yttria, 3 % by weight lanthana, 16% by weight ceria and the rest gamma alumina.
  • the ratio of the low surface area material to the high surface area material by weight is 30:70.
  • the surface area of this support material after production is 160 m 2 /g.
  • Catalyst B is produced by depositing 0.8% rhodium on the high surface area material utilized with catalyst A.
  • Catalyst C is produced by depositing 0.8% rhodium on a low surface area material comprising calcium hexaaluminate with calcium aluminate of Catalyst A. The results are shown in Figure 1.
  • the test run is described as follows: The catalyst to be tested in the form of a monolith extrusion is loaded into a test bed and tested at 700 0 C for autothermal reforming.
  • the volume of catalysts used is 1.285 cc with a total flow of gas of 642.7 liters per hour.
  • the steam to carbon ratio is 25 and the oxygen to carbon ratio is 0.7.
  • the surface area stability of each of the catalysts described above is tested by increasing the calcination temperature of the catalyst tc 1300 0 C in air. The retention of the surface area of the catalysts is compared and shown in Figure 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A catalyst for reforming hydrocarbons comprising a precious metal, preferably selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium, and combinations thereof deposited on a support, wherein the support is produced from a mixture of a low surface area material and a high surface area material.

Description

TITLE
CATALYST FOR REFORMING HYDROCARBONS
BACKGROUND OF INVENTION An embodiment of the present invention relates to catalysts for catalytic reforming of hydrocarbons utilizing a precious metal deposited upon a support, wherein the support is formed from a mixture of a low surface area material and a high surface area material. An embodiment of the present invention also relates to processes for the preparation of the reforming catalyst and processes for use of the reforming catalysts for reforming hydrocarbons.
Various processes have been utilized for the production of hydrogen from hydrocarbons. Generally, hydrocarbons react at high temperatures in the presence of water vapor on a suitable catalyst to produce hydrogen, carbon monoxide, and carbon dioxide. The process is generally referred to as steam reforming. The reaction is highly endothermic and proceeds based on the following reaction process: Cn Hm + H2O ~ CO2 + H2
Another process utilized for the production of hydrogen is referred to as partial oxidation, whereby a hydrocarbon is converted to carbon dioxide and hydrogen in the presence of oxygen utilizing a catalyst. This reaction is highly exothermic and proceeds based on the following reaction process :
Cn Hm + O2 ~ CO2 + H2 A third process for the production of hydrogen combines these two reaction processes and is called autothermal reforming. In this process the exothermic partial oxidation reaction frequently supplies the heat of reaction required for the endothermic steam reforming reaction. The reaction proceeds based on the following reaction formula:
Ca Hb + xθ2 + yH20 « aCO2 + (b/2+2a-2x) H2 + (y+2x-2a)H2O Ideally, the autothermal reaction converts all fuel to CO2 and H2. Preferably, the reaction is conducted near thermal neutral conditions. The autothermal reaction has shown particular utility as a process for use with fuel cells as autothermal reforming can be an effective method for generating hydrogen from hydrocarbon fuels while producing conventional reaction by products.
For hydrogen generation, particularly for use in a conventional low temperature fuel cell processing train, such as a proton exchange membrane (PEM) fuel cell, which is suitable for use in a stationary application or in a vehicle, such as an automobile, the hydrocarbon fuel stream can be derived from a number of conventional fuel sources, with the preferred fuel sources including natural gas, propane and LPG. In a conventional hydrogen generation system, particularly a fuel cell processing train, the hydrocarbon fuel stream is passed over and/or through a desulfurization system to be desulfurized. The desulfurized hydrocarbon fuel stream then flows into a reformer, wherein the fuel stream is converted into a hydrogen-rich fuel stream. The reformer may utilize any conventional reforming reaction such as steam reforming, partial oxidation or autothermal reforming. From the reformer the fuel stream passes through one or more heat exchangers to a shift converter where the amount of CO in the fuel stream is reduced. From the shift converter the fuel stream again passes through various heat exchangers and then through a selective oxidizer or selective methanizer having one or more catalyst beds, after which the hydrogen rich fuel stream flows to the fuel cell stack where it is utilized to generate electricity. While a number of reforming catalysts are known, improved reforming catalysts are needed which exhibit a high percentage of conversion of the feed stream into hydrogen, while retaining stability at high temperatures. One object of a preferred embodiment of the invention is to produce reforming catalysts which exhibit high conversion capacity while retaining significant surface area stability, even at high temperatures. Another object of a preferred embodiment of the invention is a process for the production of the reforming catalysts .
Another object of a preferred embodiment of the invention is a use of these catalysts for reforming conventional feed streams.
These and other objects are obtained by the catalysts of preferred embodiments of the invention, their processes of manufacture and of use.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 is a graph illustrating the CH4 conversion percentage over time for three catalysts operating at the stated conditions. The composition of the catalysts is described in the Examples. Figure 2 is a graph illustrating the retention of surface area at high calcination temperatures for the three catalysts of Figure 1. SUMMARY OF INVENTION
One of the preferred embodiments of the invention disclosed herewith is a catalyst for reforming hydrocarbons comprising one or more precious metals, selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium, and combinations thereof, with the combination of rhodium and platinum preferred, deposited on a support, wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m2/g, preferably from 1 m2/g to 10 m2/g, and from 40 to 90 percent of a high surface area material, wherein the surface area of the high surface area material is from 80 m2/g to 300 m2/g, preferably from 80 m2/g to 200 m2/g. The catalyst composition may be formed as a tablet, extrudate or powder or washcoated on a cordierite or metal monolith or on a metal or ceramic foam or similar washcoat surface.
Another embodiment is various processes for reforming a hydrocarbon feed stream utilizing the catalysts described above utilizing steam reforming, partial oxidation or autothermal reforming processes. A further embodiment is a process of forming the catalysts described above.
Detailed Description of the Invention One embodiment of the present invention is a catalyst tablet or extrudate or catalytic washcoat for reforming hydrocarbons comprising one or more precious metals, selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium, and combinations thereof, deposited upon a support, wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m2/g, and from 40 to 90 percent of a high surface area material, wherein the surface area of the high surface area material is from 80 to 300 m2/g.
The catalyst or catalytic washcoat can be utilized for a number of reforming reactions including steam reforming, catalytic partial oxidation and autothermal reforming reactions.
The catalyst or catalytic washcoat for reforming hydrocarbons comprises one or more precious metals deposited upon a support. The one or more precious metals that are deposited upon the support are selected from the group consisting of rhodium, platinum, palladium, osmium, iridium, ruthenium, rhenium and combinations thereof. In one preferred embodiment the precious metal utilized comprises rhodium utilized alone. In another preferable embodiment rhodium and platinum are utilized together. The total quantity of the precious metal (s) that is deposited upon the support for the reforming catalyst or catalytic washcoat of one embodiment of the invention is from 0.05 to 5 percent by weight, preferably from 0.1 to 3 percent by weight. In one preferred embodiment the catalyst comprises from 0.1 to 5 percent of rhodium. In another preferred embodiment the precious metal comprises a combination of from 0.1 percent to 2 percent of rhodium and from 0.05 to 3 percent of platinum.
The inventors have surprisingly discovered that a reforming catalyst with improved performance characteristics, especially high temperature stability, can be produced when the support for the precious metal is formed from a mixture comprising a low surface area material and a high surface area material. While a person skilled in the art would have anticipated that the mixture of a high surface area material and a low surface material would yield a material with a surface area in between the surface areas of the two materials, it has surprisingly been discovered that the combination yields a material with a higher than expected surface area retention at high temperatures with greater stability for the desired reactions.
For purposes of this disclosure, "low surface area" means less than 20 m2/g and preferably from 1 m2/g to 10 m2/g. One embodiment of the low surface area material of the invention includes a calcium compound combined with an aluminum compound or a MeO/alumina compound, wherein Me is selected from Ca, Sr, Ba, Mg, Mn, Ni and combinations thereof. Preferred low surface area materials include various aluminates, more preferably calcium aluminate, various hexaaluminates, more preferably selected from barium hexaaluminate, strontium hexaaluminate, manganese hexaaluminate, magnesium hexaaluminate, and combinations thereof. In a more preferred embodiment the low surface area material is a mixture of calcium aluminate and a hexaaluminate, most preferably barium hexaaluminate. In a most preferred embodiment the low surface area material mixture comprises substantially all a hexaaluminate or mixture of hexaaluminates. When calcium aluminate is utilized, the preferred calcium compound is combined with the preferred aluminum compound to form various calcium aluminates, such as
CaO- 6Al2O3, CaO -2Al2O3 and CaO-Al2O3. However, any stable calcium aluminate can be utilized.
The preferred low surface area material can be produced by conventional procedures, such as by physically mixing the calcium compound or the MeO with the alumina compound and then calcining the resultant mixture, or by purchasing the low surface area material, for example, by purchasing a Sϋd- Chemie G90 support material.
For purposes of this disclosure, a "high surface area" material has a surface area from 80 to 300 m2/g, preferably from 80 to 200 m2/g. One preferred embodiment of the high surface material comprises a high surface area alumina onto which has been impregnated various dopants, including one or more selected from the group consisting of yttria, ceria, zirconia and oxides of the lanthanides. The preferred alumina is a transitional alumina, preferably gamma alumina, with a surface area greater than 200 m2/g, preferably up to 250 m2/g or so. A particularly preferred embodiment of the high surface area material comprises a gamma alumina onto which has been impregnated ceria, yttria, and lanthana . A most preferred high surface area material comprises 1 - 5% yttria, 1 - 5% lanthana, 14 - 20% ceria with the remaining amount comprising gamma alumina, with all amounts determined by weight. Additional dopants can be added to this high surface area ceria, yttria and lanthana on alumina material including zirconia. Other dopants which may also be added include Sn, Mn, Pr, Nd, Nb, Sm, W, their oxides and mixtures thereof.
Another preferred high surface area material is a mixed metal oxide material with oxides selected from two or more of the following: zirconia, ceria, titania, silica, lanthana, praseodymia, neodymia, yttria, samaria, tungsten oxide, molybdenum oxide, calcium oxide, chromium oxide, manganese oxide and magnesium oxide. One particularly preferred high surface area mixed metal oxide combination comprises zirconia and ceria, with the preferred ratio of zirconia to ceria being 1 to 10 to 10 to 1. In a particularly preferred embodiment, praseodymia and/or neodymia are added to the ceria/zirconia support. The praseodymia and/or neodymia preferably comprise from 3% to 30% of the support, by weight. When both are present in the support, the ratio of the praseodymia to the neodymia is preferably from 1 to 1 to 3 to 1. The mixed metal oxide support high surface area material can be produced by blending together the metal oxides using conventional procedure or the mixed metal oxide can be purchased from conventional sources separately or after combination thereof.
Alternatively, the high surface area material may preferably comprise high surface area ceria, titania, or silica and mixtures thereof.
Following the production or acquisition of the low surface area material and the high surface area material, they are combined to produce the carrier for the reformer catalyst of one embodiment of the invention. Various conventional production procedures may be used for this combination. In a preferred embodiment the high surface area material and the low surface area material are physically mixed, calcined and then washcoated onto a surface by conventional washcoat procedures or extruded to form extrudates. Alternatively, the composition, after mixing and calcining, can be formed into powders or tablets. Once the high surface area and low surface area materials are formed into the support, the precious metal material is impregnated onto that support. In one preferred procedure, the precious metal is incorporated into the support material, preferably by impregnation, in the form of a precious metal salt solution. For example, when the precious metal is rhodium, the support material may be immersed in a rhodium salt solution, such as rhodium nitrate, and then dried and calcined at a temperature from 350° to 6500C for 1 to 5 hours to transform the rhodium salt to rhodium oxide. Depending on the target loading, multiple impregnation steps may be needed.
After formation of the final product, the surface area of the catalyst is preferably from 100 m2/g to 200 m2/g, more preferably from 100 m2/g to 170 m2/g, and most preferably from 150 m2/g to 160 m2/g.
The catalysts of the preferred embodiments are especially useful for reforming reactions, including steam reforming, partial oxidation and autothermal reforming, where the feed stream contains hydrocarbons, such as CH4. A quantity of steam may be added to the feed stream along with a source for oxygen. Generally the reforming conditions include a molar steam/carbon ratio of 0.1 to 10, preferably 0.5 to 5 at a temperature from 3500C to 9000C, preferably 4500C to 8000C. In one embodiment the feed stream passes over or through a bed containing the invention catalyst in the form of extrudates, tablets or powders. Alternatively, the feed stream may pass over a support onto which the catalytic material of the invention has been deposited. By- use of this catalyst, substantially higher quantities of hydrogen are produced than can be produced using conventional reforming catalysts. In addition, the catalysts have shown greater stability than prior art catalysts, especially at high temperatures. Examples The catalyst of a preferred embodiment of the invention (Catalyst A) is compared by performance with a catalyst containing the same precious metal loading but deposited solely on a high surface area material (Catalyst B) and also a catalyst with the same precious metal loading deposited on a low surface area material (Catalyst C) . Catalyst A is produced by depositing 0.8 percent rhodium on a carrier produced from a mixture of a low surface area material and a high surface area material. The low surface area material comprises calcium hexaaluminate, wherein 13% comprises calcium with the remaining amount being alumina, and the high surface area material comprises 1.5 % by weight yttria, 3 % by weight lanthana, 16% by weight ceria and the rest gamma alumina. The ratio of the low surface area material to the high surface area material by weight is 30:70. The surface area of this support material after production is 160 m2/g.
Catalyst B is produced by depositing 0.8% rhodium on the high surface area material utilized with catalyst A. Catalyst C is produced by depositing 0.8% rhodium on a low surface area material comprising calcium hexaaluminate with calcium aluminate of Catalyst A. The results are shown in Figure 1.
The test run is described as follows: The catalyst to be tested in the form of a monolith extrusion is loaded into a test bed and tested at 7000C for autothermal reforming. The volume of catalysts used is 1.285 cc with a total flow of gas of 642.7 liters per hour. The steam to carbon ratio is 25 and the oxygen to carbon ratio is 0.7. In addition, the surface area stability of each of the catalysts described above is tested by increasing the calcination temperature of the catalyst tc 13000C in air. The retention of the surface area of the catalysts is compared and shown in Figure 2. From an analysis of these tests, it is clear that the CH4 conversion by the catalyst with a support produced from a mixture of both a high surface area and a low surface area material was greater than catalysts produced wherein only a low surface area material was used to form the support or wherein only a high surface area material was used to form the support. Further, the stability of the catalyst utilizing a support produced from a mixture of both a high surface area and low surface area material had a higher surface area at higher calcination temperatures than that of the other two catalysts.
Although one or more embodiments of the invention have been described in detail, it is clearly understood that the descriptions are no way to be taken as limitations. The scope of the invention can only be limited by the appended claims .

Claims

Claims
Claim 1. A catalyst for reforming hydrocarbons comprising a precious metal, selected from the group consisting of rhodium, platinum, rhenium, palladium, osmium, iridium, ruthenium and combinations thereof, preferably comprising rhodium or rhodium and platinum, deposited on a support; wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m2/g, preferably from 1 to 10 m2/g, and from 40 to 90 percent by weight of a high surface area material, wherein the surface area of the high surface area material is from 80 to 300 m2/g, preferably from 80 to 200 m2/g.
Claim 2. The catalyst of Claim 1 wherein the low surface area material is preferably selected from the group consisting of calcium aluminate, barium hexaaluminate, magnesium hexaaluminate, strontium hexaaluminate, manganese hexaaluminate and mixtures thereof, most preferably calcium aluminate.
Claim 3. The catalyst of Claim 1, wherein the low surface area material preferably comprises an aluminum compound comprising MeO/alumina, wherein Me is selected from Ca, Sr, Ba, Mg, Mn, and combinations thereof, preferably Ba.
Claim 4. The catalyst of any of Claims 1-3, wherein the high surface area material comprises alumina promoted with oxides selected from the lanthanides, yttria, ceria, zirconia and mixtures thereof, preferably a gamma alumina combined with 1 - 5% yttria, 15 - 20% ceria and 1 - 5% lanthana, by weight.
Claim 5. The catalyst of any of Claims 1-3, wherein the high surface area material comprises a mixed metal oxide, which oxides are selected from two or more of the following: zirconia, ceria, titania, silica, lanthana, praseodymia, neodymia, yttria, samaria, tungsten oxide, molybdenum oxide, calcium oxide, chromium oxide, manganese oxide and magnesium oxide.
Claim 6. The catalyst of any of Claims 1-3, wherein the high surface area material comprises a material selected from high surface area ceria, titania, silica and mixtures thereof .
Claim 7. The catalyst of Claim 5, wherein the high surface area material preferably comprises a mixture of ceria, zirconia and one or more lanthanide oxides, most preferably praseodymium oxide and/or neodymium oxide.
Claim 8. The catalyst of any of Claims 1-7, wherein the precious metal comprises 0.05 to 5 percent, by weight of the catalyst.
Claim 9. A steam reforming reaction comprising reacting hydrocarbons in the presence of water vapor at high temperatures over a catalyst to produce hydrogen and carbon oxides, wherein the catalyst comprises a precious metal, selected from the group consisting of rhodium, platinum, rhenium, palladium, osmium, iridium, ruthenium and combinations thereof, preferably comprising rhodium or rhodium and platinum, deposited on a support; wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m2/g, preferably from 1 to 10 m2/g, and from 40 to 90 percent by weight of a high surface area material, wherein the surface area of the high surface area material is from 80 to 300 m2/g, preferably from 80 to 200 m2/g.
Claim 10. A partial oxidation reaction comprising reacting hydrocarbons in the presence of oxygen over a catalyst to produce carbon oxides and water, wherein the catalyst comprises a precious metal, selected from the group consisting of rhodium, platinum, rhenium, palladium, osmium, iridium, ruthenium and combinations thereof, preferably comprising rhodium or rhodium and platinum, deposited on a support; wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 m2/g, preferably from 1 to 10 m2/g, and from 40 to 90 percent by weight of a high surface area material, wherein the surface area of the high surface area material is from 80 to 300 m2/g, preferably from 80 to 200 m2/g.
Claim 11. An autothermal reforming reaction comprising reacting hydrocarbons in the presence of water vapor and oxygen over a catalyst to produce hydrogen and carbon oxides, wherein the catalyst comprises a precious metal, selected from the group consisting of rhodium, platinum, rhenium, palladium, osmium, iridium, ruthenium and combinations thereof, preferably comprising rhodium or rhodium and platinum, deposited on a support; wherein the support is formed from a mixture comprising from 10 to 60 percent by weight of a low surface area material, wherein the surface area of the low surface area material is less than 20 irι2/g, preferably from 1 to 10 m2/g, and from 40 to 90 percent by weight of a high surface area material, wherein the surface area of the high surface area material is from 80 to 300 m2/g, preferably from 80 to 200 mVg.
PCT/US2008/080069 2007-10-31 2008-10-16 Catalyst for reforming hydrocarbons WO2009058569A2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11/931,391 2007-10-31
US11/931,391 US20090108238A1 (en) 2007-10-31 2007-10-31 Catalyst for reforming hydrocarbons
US11/933,535 US20090118119A1 (en) 2007-11-01 2007-11-01 Water gas shift catalyst
US11/933,535 2007-11-01

Publications (2)

Publication Number Publication Date
WO2009058569A2 true WO2009058569A2 (en) 2009-05-07
WO2009058569A3 WO2009058569A3 (en) 2009-09-24

Family

ID=40225518

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2008/080069 WO2009058569A2 (en) 2007-10-31 2008-10-16 Catalyst for reforming hydrocarbons
PCT/US2008/080244 WO2009058584A2 (en) 2007-10-31 2008-10-17 A water gas shift catalyst

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2008/080244 WO2009058584A2 (en) 2007-10-31 2008-10-17 A water gas shift catalyst

Country Status (1)

Country Link
WO (2) WO2009058569A2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2008313C2 (en) * 2012-02-17 2013-09-02 Stichting Energie Water gas shift process.
WO2013135656A1 (en) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Method for reducing carbon dioxide at high temperatures on mixed metal oxide catalysts in the form of hexaaluminates
WO2013135665A1 (en) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Method for reducing carbon dioxide at high temperatures on mixed metal oxide catalysts in the form of partially substituted hexaaluminates

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5414171A (en) * 1992-02-26 1995-05-09 Catalytica, Inc. Process and washed catalyst for partially hydrogenating aromatics to produce cycloolefins
WO2000029726A1 (en) * 1998-11-13 2000-05-25 Engelhard Corporation Catalyst and method for reducing exhaust gas emissions
WO2002064251A1 (en) * 2001-02-13 2002-08-22 Sk Corporation A catalyst for selective catalytic reduction of nitrogen oxides and a method for preparing the same
WO2003043962A1 (en) * 2001-11-16 2003-05-30 Statoil Asa Heteregeneous catalyst compositions
EP1739289A1 (en) * 2004-04-19 2007-01-03 HONDA MOTOR CO., Ltd. Exhaust purifying device for internal combustion engine
WO2007088726A1 (en) * 2006-01-10 2007-08-09 Toyota Jidosha Kabushiki Kaisha Hydrogen sulfide production-suppressing member and exhaust gas-purifying catalyst
US20070238610A1 (en) * 2006-04-05 2007-10-11 Laiyuan Chen Fuel reformer catalyst

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303552A (en) * 1980-05-27 1981-12-01 W. R. Grace & Co. Diesel exhaust catalyst
JP2818171B2 (en) * 1988-09-09 1998-10-30 東洋シーシーアイ株式会社 Catalyst for steam reforming reaction of hydrocarbon and method for producing the same
US6162558A (en) * 1998-09-16 2000-12-19 General Motors Corporation Method and apparatus for selective removal of carbon monoxide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5414171A (en) * 1992-02-26 1995-05-09 Catalytica, Inc. Process and washed catalyst for partially hydrogenating aromatics to produce cycloolefins
WO2000029726A1 (en) * 1998-11-13 2000-05-25 Engelhard Corporation Catalyst and method for reducing exhaust gas emissions
WO2002064251A1 (en) * 2001-02-13 2002-08-22 Sk Corporation A catalyst for selective catalytic reduction of nitrogen oxides and a method for preparing the same
WO2003043962A1 (en) * 2001-11-16 2003-05-30 Statoil Asa Heteregeneous catalyst compositions
EP1739289A1 (en) * 2004-04-19 2007-01-03 HONDA MOTOR CO., Ltd. Exhaust purifying device for internal combustion engine
WO2007088726A1 (en) * 2006-01-10 2007-08-09 Toyota Jidosha Kabushiki Kaisha Hydrogen sulfide production-suppressing member and exhaust gas-purifying catalyst
US20070238610A1 (en) * 2006-04-05 2007-10-11 Laiyuan Chen Fuel reformer catalyst

Also Published As

Publication number Publication date
WO2009058569A3 (en) 2009-09-24
WO2009058584A2 (en) 2009-05-07
WO2009058584A3 (en) 2009-09-24

Similar Documents

Publication Publication Date Title
US20090108238A1 (en) Catalyst for reforming hydrocarbons
US6436363B1 (en) Process for generating hydrogen-rich gas
US9511351B2 (en) Catalysts for use in steam reforming processes
CN101678329B (en) Catalytic hydrogenation of carbon dioxide into syngas mixture
US8834835B2 (en) Ultra high temperature shift catalyst with low methanation
US20160257564A1 (en) Catalyst and process for thermo-neutral reforming of liquid hydrocarbons
US8540898B2 (en) Catalyst for reverse shift reaction and method for producing synthesis gas using the same
JP2008507389A (en) Promoted calcium-aluminate supported catalysts for synthesis gas generation
JP2001322803A (en) Conversion of carbon monoxide in gaseous mixtures containing hydrogen and catalysts therefor
US11311860B2 (en) Nickel catalyst for dry and low temperature steam reforming of methane
KR101979478B1 (en) High temperature combustion catalyst
DK1597196T3 (en) SELECTIVE REMOVAL OF CARBON HYDRODES SUPPLY CURRENT OLEFINES IN A HYDROGEN PREPARATION PROCEDURE
US20050238574A1 (en) High performance water gas shift catalyst and a method of preparing the same
US20090118119A1 (en) Water gas shift catalyst
Bozdağ et al. Effects of synthesis route on the performance of mesoporous ceria-alumina and ceria-zirconia-alumina supported nickel catalysts in steam and autothermal reforming of diesel
US20130085062A1 (en) Novel formulation of hexa-aluminates for reforming fuels
WO2009058569A2 (en) Catalyst for reforming hydrocarbons
Jun et al. Nickel-calcium phosphate/hydroxyapatite catalysts for partial oxidation of methane to syngas: effect of composition
Galletti et al. CO methanation as alternative refinement process for CO abatement in H2-rich gas for PEM applications
KR100448683B1 (en) POX reforming catalysts of gasoline for fuel-cell powered vehicles applications and methods for preparing catalysts
Amjad Noble Metal based Catalysts for Natural Gas Steam Reforming Activity, Endurance and Kinetics
Specchia Noble Metal based Catalysts for Natural Gas Steam Reforming
JP2009000667A (en) Catalyst for reforming ethanol to produce hydrogen and method for producing hydrogen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08843475

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08843475

Country of ref document: EP

Kind code of ref document: A2

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