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  • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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  • 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
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0213—Preparation of the impregnating solution
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  • 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
  • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
  • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
  • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/50—Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
• • 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
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1076—Copper or zinc-based catalysts
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1082—Composition of support materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to a highly active water gas conversion catalyst and a process for its preparation, and to a process for converting a gas mixture containing at least carbon monoxide and water into hydrogen and carbon dioxide over a wide temperature range using this catalyst.
• the fuel is reformed and split into CO and H 2 .
• This is followed by a water-gas conversion stage in which the CO formed is converted with water in a temperature-dependent equilibrium to C0 2 and H 2 :
• the water gas conversion stage usually occurs in two temperature stages. At temperatures between 150 ° C and 280 ° C is referred to a low temperature conversion (TTK).
• TTK low temperature conversion
• the TTK is mostly catalytically using Cu / Zn oxide catalysts. Between 280 ° C and 550 ° C is referred to a high-temperature conversion (HTK).
• HTK high-temperature conversion
• EP 1 571 125 A2 discloses a catalyst for separating carbon monoxide from hydrogen gas.
• This consists of an oxidic support material comprising zirconia, titania, alumina, silica, silica-alumina, zeolites and ceria.
• the catalytically active metal is platinum.
• there may be alkali metals such as lithium, sodium, potassium, rubidium or cesium, thus improving the activity of the catalyst for separating carbon monoxide by converting into carbon dioxide in the water-gas shift reaction.
• the catalytically active metal is present in the catalyst according to EP 1 571 125 A2 in an amount of 2% by weight.
• WO 2005/072871 A1 discloses a catalyst for the water gas shift reaction which contains metallic particles and particles of metal oxide. Suitable metal oxides are, for example, cerium oxide, titanium dioxide, iron oxide, manganese oxide or zinc oxide. Suitable metal particles are, for example, gold or platinum and are present in an amount of from 0.5 to 25% by weight with respect to the oxidic material.
• US 2006/0002848 A1 discloses a catalyst comprising a support material of, for example, alumina, titania, silica, zirconia or a combination thereof.
• alkali metals or alkaline earth metals can be present, as well as metals selected from lead, bismuth, polonium, magnesium, titanium vanadium chromium, manganese iron, nickel or cobalt, etc.
• catalytically active metals are platinum, palladium, copper, rhodium, etc.
• EP 1 908 517 A1 discloses a catalyst for converting H 2 O / carbon monoxide into hydrogen and the use of this catalyst for hydrogen enrichment of a stream used to supply a fuel cell.
• This catalyst is a solid comprising an active phase containing elements of the eighth group on a support material consisting of alumina, silica, zirconia or mixtures thereof and a promoter from the group of rare earths, for example lanthanum or cerium.
• US 2005/0207958 A1 discloses a process for reducing the amount of carbon monoxide in a water gas shift reactor without formation of methane.
• a catalyst is used which has a carrier material based on cerium oxide and zirconium oxide or cerium oxide and lanthanum oxide. Promoters which avoid methanation use copper, manganese, iron compounds or combinations thereof. Other promoters may be alkali or alkaline earth metals.
• the amount of platinum present on the catalyst is at least 1% by weight.
• US 2005/0191224 A1 discloses a catalyst for separating carbon monoxide from hydrogen gas.
• the catalyst used for this purpose has a support of metal oxide, a platinum component and an alkali metal, applied to this support.
• zirconia, titania, alumina, silica, silica-alumina, zeolites or ceria are suitable as the carrier material. It was therefore the task of finding an active catalyst which can be used over a wide temperature window and in this case forms little methane.
• the catalyst should have the lowest possible noble metal entry.
• Noble metal-containing catalysts are prepared either by impregnation of a shaped carrier material with metal salt solutions of the noble metal component or by impregnation of the carrier powder and subsequent shaping.
• the object of the invention was therefore further to provide a method in which the least possible precious metal component is deposited at inaccessible to the reaction points.
• a catalyst comprising at least one noble metal in an amount of 0.001 to 1, 10 wt .-%, based on the total weight of the catalyst, at least one alkali and / or alkaline earth metal and at least one dopant selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof, on a support material.
• Further objects of the present invention are a process for the preparation of such a catalyst and a process for the conversion of a gas mixture containing at least carbon monoxide and water, to hydrogen and carbon dioxide, using such a catalyst.
• the catalyst of the invention comprises at least one noble metal and at least one alkali and / or alkaline earth metal, each in specific amounts, as well as a doping with at least one element selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof, on a support material.
• the at least one noble metal is preferably selected from the group consisting of Au, Pt, Pd, Rh and Ru. Particular preference is given to using Pt. Also advantageous are combinations of Pt with one or more of said noble metals or combinations of one or more of said precious metals without Pt.
• the present invention particularly preferably relates to the catalyst according to the invention, wherein the noble metal is selected from the group consisting of Au, Pt, Pd, Rh, Ru and mixtures thereof. Very particular preference is given to using Pt as the noble metal, and it is particularly preferable for Pt to be the only noble metal on the catalyst according to the invention.
• the concentration of the at least one noble metal according to the invention is advantageously from 0.001 to 1, 10 wt .-%, preferably 0.01 to 1, 00 wt .-%, particularly preferably 0.1 to 0.99 wt .-%, for example 0.1 to 0.96 wt .-%, each based on the total weight of the catalyst. Due to the specific combination of features of the catalyst according to the invention, it is possible to be able to use very small amounts of expensive noble metal, and yet to achieve a high catalytic activity. According to the invention, Li, Na, K, Rb, Cs, Mg, Ca and / or Sr are preferably used as at least one alkali metal and / or alkaline earth metal. Particular preference is given to Li, Na, K and Rb, in particular Na or K.
• the present invention therefore particularly preferably relates to the catalyst according to the invention, wherein the alkali and / or alkaline earth metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof.
• the concentration of the at least one alkali metal and / or alkaline earth metal in a preferred embodiment is 1.0 to 4.0% by weight, more preferably 1.2 to 4.0% by weight, most preferably 1.8 to 3 , 5 wt .-%, particularly preferably 2.0 to 3.2 wt .-%, each based on the total weight of the catalyst. In a further preferred embodiment, from 1.2 to 3.5% by weight, based on the total weight of the catalyst, of K or Na is used. Therefore, in a preferred embodiment, the present invention relates to the catalyst according to the invention, wherein the at least one alkali and / or alkaline earth metal in an amount of 1, 0 to 4.0 wt .-%, based on the total catalyst, is present.
• the catalyst according to the invention contains at least one doping agent selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof. Very particular preference is given to using iron as doping agent according to the invention. Particularly preferred is exclusively Fe used as a dopant.
• the at least one doping agent, in particular iron is present in a concentration of generally 0.01 to 5% by weight, preferably 0.05 to 2.5% by weight, particularly preferably 0.1 to 1, 5 wt .-%, each based on the total weight of the catalyst, before.
• the catalyst according to the invention may contain further dopants, for example rare earth metals and / or main group elements of groups 13 to 15. Such further dopants may have concentrations of altogether at most 15% by weight. exhibit.
• Suitable carrier materials according to the invention are all materials which can usually be used for this purpose in catalyst chemistry and which have a sufficiently high BET surface area.
• the BET surface area should be at least 50 m 2 / g.
• the carrier materials containing combinations of lanthanide oxides and transition metals particularly preferably Ce / Zr oxide.
• the ratio of Ce oxide to Zr oxide should advantageously be from 15 to 25 to 85 to 75 wt .-%, each based on the total weight of the carrier material.
• the Ce / Zr oxide support material contains dopants of further oxides, for example Al 2 O 3 and / or La oxide.
• a preferred ratio of Al 2 O 3 to Ce / Zr oxide according to the invention is 5 to 20 to 95 to 80, more preferably 8 to 12 to 92 to 88, for example 10 to 90.
• the amount of La oxide (La 2 O 3 ) may for example be 1 to 10 wt .-%, preferably 3 to 8 wt .-%, particularly preferably 4 to 6 wt .-%, each based on the total weight of the carrier material ,
• the present invention therefore particularly preferably relates to the catalyst according to the invention, wherein the support material contains at least Ce and / or Zr.
• the present invention relates to the catalyst according to the invention, wherein the support material additionally contains La and / or Al.
• the present invention relates to the catalyst according to the invention, wherein Pt is present as a noble metal, the alkali and / or alkaline earth metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof, the Dopant is Fe, and a carrier material containing Ce and / or Zr is present.
• Pt is present as a noble metal
• the alkali and / or alkaline earth metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof
• the Dopant is Fe
• a carrier material containing Ce and / or Zr is present.
• the present invention particularly preferably relates to this catalyst according to the invention, wherein the support material additionally contains La.
• the present or optionally present in the catalyst according to the invention components d. H. the said noble metals, alkali metals and / or alkaline earth metals, dopants and support materials are present in elemental and / or oxidic form.
• the present invention relates to the catalyst according to the invention, wherein the at least one noble metal, in particular Pt, in an amount of 0.001 to 1, 10 wt .-%, preferably 0.01 to 1, 00 wt .-%, especially preferably 0.1 to 0.99 wt .-%, for example 0.1 to 0.96 wt .-%, the at least one alkali and / or alkaline earth metal, in particular Na or K, in an amount of 1, 2 to 4 , 0 wt .-%, preferably 1, 8 to 3.5 wt .-%, particularly preferably 2.0 to 3.2 wt .-%, and the at least one dopant, in particular Fe, in an amount of 0.05 to 2.5 wt .-%, particularly preferably 0.1 to 1, 5 wt .-%, each based on the total weight of the catalyst, is present, and the carrier material contains at least Ce and / or Zr. Very particularly preferred embodiments of the present invention
• a catalyst which, used in a shift reaction, has a very high reactivity, combined with a very high efficiency, shows.
• the high reactivity of the catalysts according to the invention can be demonstrated, for example, by the fact that said shift reaction takes place even at a relatively low temperature with almost complete thermodynamically possible conversion.
• the particularly high efficiency of the catalyst according to the invention can be demonstrated by the fact that the catalyst in the shift reaction has little tendency to methanation, ie. h., That only a small proportion of the hydrogen formed is converted by the formation of methane.
• the catalyst according to the invention can be prepared by impregnating the individual components onto the support material.
• the active components are applied to powdered carrier material, which is then at least partially kneaded and extruded. It is also possible that one combines the production variants with each other and, for example, only a part of the active components applied to the powdered carrier material and thus kneaded and extruded and the remaining active components or their remaining subsets are then impregnated.
• the active components are preferably used in the form of their salts or their oxides.
• Suitable salts according to the invention are, for example, oxides, nitrates, hydroxides, acetates, acetylacetonates, carbonates, nitrosyl nitrates or halides, such as fluorides, chlorides, bromides and iodides.
• the components are in an advantageous embodiment soaked in the carrier material. Since due to conditions to be observed, such as pH, concentrations, etc., usually different metal salts can not be impregnated in parallel, the preparation of a catalyst with different promoters is often but not exclusively in a variety of impregnation steps, for example, two steps of impregnation, carried out sequentially become.
• the application of the active components by impregnation on the carrier material can be carried out in the usual manner, such. B. as a washcoat on a monolith.
• the active material is first applied at least in part to the carrier material, preferably powdered carrier material, and then kneaded and then extruded, the kneading and extrusion of the carrier material with the active materials can be carried out in the usual manner with known apparatuses.
• the carrier material preferably powdered carrier material
• the present invention therefore relates in particular to a process for the preparation of the catalyst according to the invention, wherein the at least one noble metal, at least one alkali and / or alkaline earth metal, and the at least one dopant are applied to the support material as a solution or dispersion or a part or all of the at least one noble metal, the at least one alkali and / or alkaline earth metal and / or the at least one doping agent are applied to a carrier material as a solution or dispersion and this carrier material is mixed with the remaining part of the components.
• moldings from pulverulent raw materials can be carried out by customary methods known to the person skilled in the art, such as, for example, tableting, aggregation or extrusion, as described i.a. in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp. 414-417.
• auxiliaries known to the person skilled in the art such as binders, lubricants and / or solvents, may be added.
• the described production methods are simple and inexpensive.
• the inventive catalyst is highly active with respect to the shift reaction, but suppresses the methanation reaction, for example by the catalyst according to the invention a methane content of less than 100 ppm, preferably less than 50 ppm (each at 350 ° C) and less than 500 ppm, preferably less than 300 ppm, (each at 450 ° C) reached.
• the catalyst described can be used in the process according to the invention for the conversion of a gas mixture containing at least carbon monoxide and water to hydrogen and carbon dioxide.
• the process can be carried out under the usual conditions of a conversion reaction, both in the TTK range at temperatures of usually 150-280 ° C., and in the HTK range at temperatures of usually 280-550 ° C. Due to the low tendency of methanation of the catalyst according to the invention even at high temperatures, this is particularly recommended for the HTK, are unsuitable in the previous catalysts of the prior art.
• the conversion reaction according to the invention in a temperature range of 180 to 550 ° C. It is thus possible and advantageous, both in the stage the HTK and in the stage of TTK use the catalyst of the invention.
• the process according to the invention for reducing carbon monoxide (CO) by the process of a conversion reaction on the highly active conversion catalyst according to the invention is carried out in customary apparatuses and under customary conditions for carrying out a conversion reaction, as described, for example, in the Handbook of heterogeneous catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, pages 354-355, and with overflow of the catalyst with a CO and water-containing process gas.
• the process gas used is a gas mixture, in addition to carbon monoxide and water, which are reacted in the conversion reaction described, usually also other gases such. As hydrogen, carbon dioxide and nitrogen.
• the present invention therefore also relates to the use of the catalyst according to the invention, the conversion of carbon monoxide and water to carbon dioxide and hydrogen.
• the present invention relates to a process for the conversion of a gas mixture containing at least carbon monoxide and water, to carbon dioxide and hydrogen, wherein a catalyst according to the invention is used.
• FIG. 1 shows an exemplary measuring scheme.
• the abbreviations have the following meanings:
• Catalysts and catalysts according to the invention which serve as a comparison are prepared by the following processes:
• the preparation of the catalysts according to the invention and the comparative catalysts can be carried out by impregnation, as shown by the following example for the preparation of a catalyst:
• the required amount of iron nitrate is dissolved in the stated amount of platinum nitrate solution and distilled with H 2 0. diluted to a volume corresponding to 90% of the water absorption of the Ce / Zr support material.
• the strands are presented and spray-impregnated while circulating with the platinum / iron nitrate solution. After soaking, the strands are circulated for a further 5 minutes, then dried and then calcined.
• potassium hydroxide is distilled with H 2 0. diluted to a volume equivalent to 90% of the water uptake of the resulting Pt / Fe doped strands. These strands are then spray-impregnated with the resulting dilute potassium hydroxide solution with constant circulation. After soaking, the strands are recirculated for another 5 minutes, then dried and then calcined. Drying: 4h at 200 ° C in a convection oven
• the preparation of the catalysts according to the invention and of the comparative catalysts can be carried out by kneading, as shown by the following example for the preparation of a catalyst:
• Kneader submitted The least with H 2 0. Nitric acid diluted to 20 ml total volume is added slowly and kneaded for 10 minutes. Then the iron nitrate is dissolved in the platinum nitrate solution, destilled with H 2 0. diluted to 30 ml total volume, added and kneaded for 5 minutes. Subsequently, the potassium hydroxide solution is added undiluted and kneaded again for 10 minutes. H 2 0 dist. Is added in small portions until a plastic mass is obtained. stands. The plastic mass is deformed by means of an extruder to 1, 5 mm strands.
• Catalyst installation 15 mL catalyst (bed) or 8 to 12 mL (volume of a monolith) are installed in the reactor,
• composition of the reaction gas used for the testing is:
• test method M 26% by weight of H 2 O
• the catalyst loading GHSV during testing is 12,279 / h.
• This test variant is referred to below as test method M.
• the temperature program can be changed, for example, by reducing the final temperature to 380 ° C. with the starting temperature unchanged for method M and the heating rate (° C./min).
• Heating convection oven with temperature range up to max. 600 ° C,
• Linseis-36 channel recorder as interface for data storage
• Table 1 shows the results of the catalysts according to the invention and the catalysts prepared for comparison: Table 1: Results of the various catalysts according to the invention and the catalysts for comparison

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• 2011
  • 2011-08-25 WO PCT/IB2011/053729 patent/WO2012025897A1/de active Application Filing
  • 2011-08-25 EP EP11819508.0A patent/EP2608882A4/de not_active Withdrawn
  • 2011-08-25 JP JP2013525407A patent/JP5961166B2/ja not_active Expired - Fee Related
  • 2011-08-25 KR KR1020137007248A patent/KR101854941B1/ko not_active Expired - Fee Related
  • 2011-08-25 CA CA2805259A patent/CA2805259A1/en not_active Abandoned

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