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WO2009058584A2 - Catalyseur de conversion de gaz à l'eau - Google Patents

Catalyseur de conversion de gaz à l'eau Download PDF

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Publication number
WO2009058584A2
WO2009058584A2 PCT/US2008/080244 US2008080244W WO2009058584A2 WO 2009058584 A2 WO2009058584 A2 WO 2009058584A2 US 2008080244 W US2008080244 W US 2008080244W WO 2009058584 A2 WO2009058584 A2 WO 2009058584A2
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WO
WIPO (PCT)
Prior art keywords
surface area
water gas
gas shift
support
shift catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2008/080244
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English (en)
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WO2009058584A3 (fr
Inventor
Chandra Ratnasamy
Jon P. Wagner
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Sued Chemie Inc
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Sued Chemie Inc
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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 Sued Chemie Inc filed Critical Sued Chemie Inc
Publication of WO2009058584A2 publication Critical patent/WO2009058584A2/fr
Publication of WO2009058584A3 publication Critical patent/WO2009058584A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
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    • B01J23/56—Platinum group metals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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
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    • 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

  • the invention relates to water gas shift catalysts. More particularly, one embodiment of the invention relates to a water gas shift catalyst comprising a precious metal deposited upon a support, wherein the support is produced from a mixture of a low surface area material, such as an aluminate, and a high surface area material, such as a mixed metal oxide. A further embodiment adds various dopants and/or other additives to the catalyst and/or the support for the catalyst to enhance its performance, particularly an alkali metal dopant.
  • Fuel cell power plants that utilize a fuel cell stack for producing electricity from a hydrocarbon fuel are well known.
  • a low temperature fuel cell processing train such as a proton exchange membrane fuel cell, which is suitable for use in a stationary application or in a vehicle, such as an automobile.
  • the hydrocarbon fuel for such fuel cell stacks can be derived from a number of conventional fuel sources, with preferred fuel sources including, but not limited to, natural gas, propane and LPG.
  • the hydrocarbon fuel In order for the hydrocarbon fuel to be useful in the fuel cell stack, it must first be converted to a hydrogen rich fuel stream. After desulfurization, the hydrocarbon fuel stream typically flows through a reformer, wherein the fuel stream is converted into a hydrogen rich fuel stream. This converted fuel steam contains primarily hydrogen, carbon dioxide, water and carbon monoxide. The quantity of carbon monoxide can be fairly high, up to 15% or so.
  • Anode electrodes which form part of the fuel cell stack, are adversely affected by high levels of carbon monoxide. Accordingly, it is necessary to reduce the quantity of carbon monoxide in the fuel stream prior to passing it to the fuel cell stack. Such reduction in the quantity of carbon monoxide is typically performed by passing the fuel stream through a water gas shift converter, and possibly other reactors, such as a selective oxidizer, prior to passing the fuel stream to the fuel cell stack. In addition to reducing the quantity of carbon monoxide in the fuel stream, water gas shift converters also increase the quantity of hydrogen in the fuel stream.
  • Water gas shift reactors are well known and typically contain an inlet for introducing the fuel stream containing carbon monoxide into a reaction chamber, a down stream outlet, and the catalytic reaction chamber, which is located between the inlet and outlet.
  • the catalytic reaction chamber typically contains catalytic material for converting at least a portion of the carbon monoxide and water in the fuel stream into carbon dioxide and hydrogen.
  • the water gas shift reaction is an exothermic reaction represented by the following formula:
  • water gas shift catalysts typically contain chromium, copper or noble metals placed on a support.
  • the noble metals comprise Pt and Re on a conventional support.
  • high pressure or “higher pressure” means pressures above 50 psi (3.4 bar) .
  • fuel cells may be subjected to a number of start up and shut down cycles over the life of the water gas shift catalyst.
  • Conventional water gas shift catalysts are not designed to perform well under such conditions.
  • an improved water gas shift catalyst comprising a precious metal deposited upon a support, wherein the support is produced from a mixture comprising a low surface area material, preferably an aluminate, and _
  • a high surface area material preferably a mixed metal oxide.
  • a further embodiment of the invention comprises an improved water gas shift catalyst comprising a precious metal deposited upon a support, wherein the support is produced from a mixture comprising a low surface area material, preferably an aluminate, a high surface area material, preferably a mixed metal oxide and an alumina, preferably a transitional phase, high surface area alumina, more preferably a gamma alumina.
  • a further embodiment of the invention comprises an improved water gas shift catalyst comprising a precious metal deposited upon a support, wherein the support is produced from a mixture comprising a low surface area material, preferably an aluminate, a high surface area material, preferably a mixed metal oxide, and a transitional phase, high surface area alumina, preferably gamma alumina, wherein an alkali or alkaline earth metal dopant is added to the catalyst and/or rhe support.
  • a low surface area material preferably an aluminate
  • a high surface area material preferably a mixed metal oxide
  • a transitional phase high surface area alumina, preferably gamma alumina
  • a further embodiment of the invention comprises a water gas shift reaction whereby at least a portion of the carbon monoxide and water in a fuel stream is converted to hydrogen and carbon dioxide by utilization of catalyst comprising a precious metal deposited on a support, wherein the support is produced from a mixture of a low surface area material and a high surface area material.
  • a further embodiment of the invention comprises a process for the preparation of an improved water gas shift catalyst comprising preparing or selecting a support, wherein the support comprises a mixture of a low surface area material, preferably an aluminate, more preferably a hexaaluminate, and a high surface area material, preferably a mixed metal oxide, wherein the mixed metal oxide is selected from cerium oxide, zirconium oxide, titanium oxide, silicon oxide, neodymium oxide, praseodymium oxide, yttrium oxide, samarium oxide, lanthanum oxide, tungsten oxide, molybdenum oxide, calcium oxide, chromium oxide, magnesium oxide and mixtures thereof.
  • the mixed metal oxides comprise zirconia and ceria.
  • a precious metal preferably platinum, and preferably one or more dopants, more preferably an alkali or alkaline earth metal oxide, most preferably an alkali metal oxide, are deposited or impregnated on the support or the catalyst.
  • Figure 1 is a graph illustrating the CO conversion percentage over time for two water gas shift catalysts operating at a pressure of 225 psig (15.5 bar) and a temperature of 350 0 C, wherein one catalyst contains Pt and Re on a support produced from a mixture of cerium oxide and zirconium oxide and the other catalyst has the same composition but without Re.
  • Figure 2 is a graph comparing the CO conversion over time of several water gas shift catalysts, wherein the catalysts contain Pt on various compositions which form the support thereof, wherein the water gas shift reaction is conducted at a pressure of 225 psig (15.5 bar) and a temperature of 35O 0 C.
  • Figure 3 is a graph comparing the CO conversion over time of several water gas shift catalysts, wherein the catalysts contain Pt deposited on various compositions as the support, wherein an alkali metal dopant (either Na or K) is added to the composition of two of the catalysts and wherein the water gas shift reaction is conducted at a pressure of 225 psig (15.5 bar) and a temperature of 350 0 C.
  • an alkali metal dopant either Na or K
  • the water gas shift catalyst of one embodiment comprises a precious metal deposited upon a support, wherein the support comprises a mixture of a low surface area material and a high surface area material.
  • low surface area means less than 20 m 2 /g and preferably about 2 - 15 m 2 /g.
  • the low surface area material comprises an aluminate, preferably a hexaaluminate, wherein the cation for the hexaaluminate is selected from barium, calcium, potassium, manganese, magnesium, hafnium, scandium, zirconium, yttrium, cerium, lanthanum, praseodymium, neodymium, strontium and mixtures thereof.
  • a particularly preferred hexaaluminate comprises barium hexaaluminate. Methods for preparing such hexaaluminates are known.
  • low surface area materials include various aluminates, preferably calcium aluminate, and various low surface area zirconium, titanium and aluminum compounds and mixtures thereof. Combined with the low surface area material to form the support of the improved water gas shift catalyst is a high surface area material.
  • high surface area means from about 80 to about 250 m 2 /g and preferably from about 80 to 200 m 2 /g.
  • One preferred high surface area material is a mixed metal oxide, which oxides may be selected from two or more of the following: zirconia, ceria, titania, silica, lanthana, praseodymium oxide, neodymium oxide, yttria, samarium oxide, tungsten oxide, molybdenum oxide, calcium oxide, chromium oxide, manganese oxide and magnesium oxide.
  • One particularly preferred mixed metal oxide combination comprise zirconia and ceria with the preferred ratio of zirconia to ceria being about 1 to about 10 to about 10 to about 1.
  • praseodymia and/or neodymia are added to the ceria/zirconia support.
  • the praseodymia and/or neodymia preferably comprises from about 3% to about 30% of the support, by weight. When both are present in the support, the ratio of the praseodymia to the neodymia is from 1 to 1 to about 3 to 1.
  • the mixed metal oxide portion of the support can be produced by blending together the metal oxides using conventional procedures or the mixed metal oxide component can be purchased from conventional sources separately or after combination of the separate metal oxides.
  • the high surface area material may comprise a promoted alumina, preferably gamma alumina, promoted with dopants including oxides selected from cerium, zirconium, lanthanum, yttrium, praseodymium, neodymium, samarium, tungsten, and molybdenum and the like and mixtures thereof.
  • a particularly preferred high surface area material comprises gamma alumina promoted with ceria, lanthana and yttria.
  • the high surface area material comprises a high surface ceria, titania, or silica and mixtures thereof.
  • the low surface area material and the high surface area material are physically mixed by conventional procedures.
  • Conventional liquids, such as water and acetic acid are preferably added to the mixture of solid materials to permit them to be processed, for example, by extrusion, to form extrudates or to form a slurry to be washcoated on a conventional honeycomb.
  • the percentage of the high surface area material and low surface area material in the support ranges from about 10% to 90%, by weight.
  • the low surface area material comprises about 20 to 40%, by weight
  • the high surface area material comprises from about 80% to about 40% of the support, by weight.
  • the ratio of the low surface area material to the high surface area material is unchanged.
  • there is added to the mixture of the low surface area material and the high surface area material up to about 40%, by weight, of an alumina.
  • the preferred alumina is a transitional phase, high surface area alumina, more preferably a gamma alumina, with a surface area greater then about 200 m 2 /g.
  • the alumina is blended with the low surface area material and the high surface area material to assist in binding the low surface area material and the high surface area material together.
  • support is the support for the precious metal and other dopants and does not refer to the use of a monolith or other such mechanical support used with a catalytic coating.
  • an alkali or alkaline earth metal oxide is added to the support as a dopant, preferably comprising from about 0.2 to about 10 % by weight, and more preferably 1.0 to 1.5 %, by weight of the support.
  • the dopant is an alkali metal oxide selected from sodium, potassium, cesium and rubidium and mixtures thereof with sodium and/or potassium oxides particularly preferred.
  • the dopant can be added by conventional procedures, such as impregnation.
  • the alkali or alkaline earth metal dopant is impregnated into the support after formulation of the support. It has been surprisingly discovered that the addition of an alkali metal oxide dopant to the catalyst extends the activity and selectivity of the catalyst even after repeated start up and shut down cycles .
  • the precious metal which is deposited upon the support comprising a low surface area material and a high surface area material, includes any of the precious metals, such as platinum, rhodium, rhenium, palladium, osmium, iridium, ruthenium and combinations thereof, and preferably platinum.
  • the precious metal when the catalyst is used in a water gas shift reaction at higher pressures and temperatures above about 180 0 C, the precious metal is preferably only Pt and does not also include other precious metals, especially rhenium. While other precious metals can be used alone or in combination, the best performance for this preferred embodiment under these conditions is obtained by use of platinum alone. Fewer unwanted by products are produced ⁇
  • the quantity of the precious metal deposited upon the support is from about 0.01 to 5%, by weight, preferably from about 0.01 to about 1%, by weight.
  • additional dopants are added to the catalyst with the precious metal, which dopants are selected from Ga, Nd, Pr, W, Ge, Au, Ag, and Fe, and their oxides and mixtures thereof, with Ga and Nd and their oxides preferred.
  • the precious metal and dopants are impregnated onto the support material in the form of a salt solution.
  • a platinum salt solution such as tetra amine platinum hydroxide
  • its surface area is preferably from about 30 to about 100 m 2 /g, more preferably from about 40 to about 80 m 2 /g.
  • the water gas shift catalyst of the preferred embodiments preferably is produced in the form of moldings, especially in the form of spheres, pellets, rings, tablets or extruded products, in which the later are formed mostly as solid or hollow objects in order to achieve higher geometric surfaces with a simultaneously low resistance to flow.
  • monoliths coated with the catalytic materials are also preferred embodiments .
  • the catalyst is preferably employed in a process in which carbon monoxide and steam are converted to hydrogen and carbon dioxide at a temperature above 180 0 C, preferably above 250 0 C, more preferably above 350 0 C and most preferably above 400 0 C ranging up to about 550 0 C and under pressures above ambient, preferably above about 50 psi (3.4 bar) more preferably above about 100 psi (6.9 bar), and most preferably above about 150 psi (10.3 bar) up to about 400 psi, (28 bar) .
  • the carbon monoxide comprises from about 1 to about 15% of the feed stream and the molar ratio of the steam to the dry gas is from about 0.1 to about 5.
  • Catalysts in the form of either a monolith or extrusions are produced for use in a reactor.
  • the conditions of the reactor are a dry gas inlet comprising 10% CO, 15% CO 2 , 10% N 2 , with the remaining amount comprising hydrogen.
  • the temperature within the reactor is set at 35O 0 C.
  • the pressure is 225 psig (15.5 bar) with a DGSV of 27,200 1/hr, a wet gas space velocity of 40,000 1/hr and a S/G ratio of 0.47.
  • the gas stream is passed over a catalyst bed containing 8 ccs of the catalyst under these conditions for various hours on stream.
  • the time on stream is shown in Figures 1 - 3.
  • the Figures disclose the CO conversion percentage over time for each catalyst tested.
  • a ceria/zirconia support is purchased from Rhodia comprising 80% ceria and 20% zirconia. Impregnated on this support is either 0.5% platinum in the form of platinum oxide, plus 0.5% rhenium in the form of rhenium oxide or 0.5% platinum alone.
  • a water gas shift reaction for each catalyst is run at the stated conditions for the stated hours on stream.
  • the catalyst containing platinum and rhenium exhibited a higher CO conversion than the catalyst containing only platinum on the ceria/zirconia _
  • Three catalysts were prepared with differing supports: 1) 60% ceria/zirconia, ratio of ceria to zirconia 80:20, and 40% barium hexaaluminate, 2) 100% ceria/zirconia, ratio of ceria to zirconia 80:20, and 3) 100% barium hexaaluminate.
  • Each catalyst was impregnated with from 0.43% to 0.52% platinum.
  • the catalyst with the ceria/zirconia support contained 0.43% platinum, by weight .
  • the catalyst with the barium hexaaluminate support contained 0.52% platinum, by weight.
  • the catalyst with a blend of ceria/zirconia and barium hexaaluminate contained 0.49% platinum, by weight.
  • a water gas shift reaction is run for the stated hours on stream at the conditions shown in Figure 2 for each of the catalysts.
  • the catalyst containing a support comprising a combination of ceria/zirconia and barium hexaaluminate exhibited a substantial conversion of CO, at least 20% greater than the catalyst containing only a ceria/zirconia support or a catalyst containing only a barium hexaaluminate support.
  • FIG. 3 The purpose of Figure 3 is to show the impact of adding an alkali metal dopant to various catalysts.
  • One catalyst contained 0.5 % sodium and 0.5% platinum on a support comprising 60% ceria/zirconia (ratio: 80% ceria to 20% zirconia) and 40% barium hexaaluminate.
  • Another catalyst contained 0.5% platinum on a support comprising 60% ceria/zirconia (ratio: 80% ceria to 20% zirconia) and 40% barium hexaaluminate to which has been added 0.5% potassium, by- weight.
  • a catalyst is prepared containing 0.5% platinum on a support comprising 60% ceria/zirconia (ratio: 80% ceria to 20% zirconia) and 40% barium hexaaluminate without any alkali or alkaline earth metal dopant.
  • Another catalyst is prepared containing 0.5% platinum on a support comprising only 60% ceria and 40% zirconia.
  • a water gas shift catalyst reaction is run for each catalyst at. the stated conditions for the stated hours on stream. As is clear from Figure 3, the conversion of CO is highest in catalysts containing an alkali metal dopant.
  • catalysts utilizing a support prepared from a mixture comprising a high surface area material and a low surface area material when operated at higher pressures, produced little or no higher molecular weight hydrocarbons or by- products.
  • the inventors have also discovered that the performance of these catalysts may be improved by the addition of a high surface area transitional alumina, preferably gamma alumina, as an additional component of the support.
  • the inventors have also discovered that the life of these catalysts can be extended, especially when the catalysts are exposed to repeated start up and shut down cycles, when an alkali metal dopant is added.
  • the inventors have also discovered that the performance of these catalysts may be further improved by impregnating the catalysts with dopants selected from Ga, Nd, Pr, W, Ge, Au, Fe and their oxides and mixtures thereof. ⁇

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Abstract

L'invention porte sur un catalyseur de conversion de gaz à l'eau comprenant un métal précieux déposé sur un support, le support étant préparé à partir d'un mélange comprenant une matière de faible surface spécifique, telle qu'un aluminate, en particulier un hexaaluminate, et une matière de surface spécifique élevée, telle qu'un oxyde métallique mélangé, en particulier un mélange de zircone et d'oxyde de cérium, à laquelle peuvent être ajoutés un ou plusieurs composants parmi une alumine de transition de surface spécifique élevée, un dopant métal alcalin ou alcalino-terreux et un dopant supplémentaire choisi parmi Ga, Nd, Pr, W, Ge, Au, Ag, Fe, leurs oxydes et leurs mélanges.
PCT/US2008/080244 2007-10-31 2008-10-17 Catalyseur de conversion de gaz à l'eau Ceased WO2009058584A2 (fr)

Applications Claiming Priority (4)

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

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WO2009058584A3 WO2009058584A3 (fr) 2009-09-24

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2013135656A1 (fr) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal (mélange de métaux des terres rares) sous forme d'hexaaluminates
WO2013135665A1 (fr) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal sous forme d'hexaaluminates partiellement substitués
US20150014595A1 (en) * 2012-02-17 2015-01-15 Stichting Energieonderzoek Centrum Nederland Water gas shift process

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WO2002064251A1 (fr) * 2001-02-13 2002-08-22 Sk Corporation Catalyseur pour la reduction catalytique selective des oxydes d'azote et procede de preparation dudit catalyseur
GB0127517D0 (en) * 2001-11-16 2002-01-09 Statoil Asa Catalysts
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150014595A1 (en) * 2012-02-17 2015-01-15 Stichting Energieonderzoek Centrum Nederland Water gas shift process
US9260302B2 (en) * 2012-02-17 2016-02-16 Stichting Energieonderzoek Centrum Nederland Water gas shift process
WO2013135656A1 (fr) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal (mélange de métaux des terres rares) sous forme d'hexaaluminates
WO2013135665A1 (fr) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal sous forme d'hexaaluminates partiellement substitués

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