EP3274088A1 - Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone - Google Patents

Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone

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Publication number
EP3274088A1
EP3274088A1 EP16714331.2A EP16714331A EP3274088A1 EP 3274088 A1 EP3274088 A1 EP 3274088A1 EP 16714331 A EP16714331 A EP 16714331A EP 3274088 A1 EP3274088 A1 EP 3274088A1
Authority
EP
European Patent Office
Prior art keywords
catalytically active
active composition
ruthenium
weight
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.)
Pending
Application number
EP16714331.2A
Other languages
German (de)
English (en)
Inventor
Andrian Milanov
Ekkehard Schwab
Mike Hoffmann
Stefan Kotrel
Stefan Altwasser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hulteberg Chemistry & Engineering AB
Original Assignee
BASF SE
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
Application filed by BASF SE filed Critical BASF SE
Publication of EP3274088A1 publication Critical patent/EP3274088A1/fr
Pending legal-status Critical Current

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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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
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    • B01J23/46—Ruthenium, rhodium, osmium or iridium
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    • 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
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    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/37—Lanthanides
    • B01J2523/3706—Lanthanum
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a catalytic composition and a process for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing streams, in particular for use in fuel cell systems.
  • PEM Polymer Electrolyte Membrane
  • CO carbon monoxide
  • a residual concentration of CO in the gas stream generally remains in the range of 0.25 to 1.5% by volume, depending on the process design and temperature.
  • a CO removal can be achieved up to 2,500 ppm.
  • the CO content in the hydrogen-rich gas must be further reduced in order to avoid poisoning of the anode catalyst; Guideline values are here between maximally 10 and 50 ppm.
  • the CO methanation (hydrogenation of carbon monoxide to methane) is carried out according to the reaction equation:
  • CO + 3H 2 -> CH 4 + H 2 0 ⁇ -206.2 kJ / mol
  • the particular challenge for selective CO methanation is that CO should preferably be hydrogenated and not CO2, as this would consume more hydrogen.
  • the CO concentration in the reformate is about 2500 ppm to 15,000 ppm, while the C0 2 content of about 15 to 25 vol .-% is an order of magnitude above the CO content. Accordingly, a CO-selective catalyst for the realization of low CO concentrations, as used for z. B. PEM fuel cells are required, indispensable.
  • EP-A-1174486 combines a methanation stage with a selective oxidation unit for the purpose of lower oxygen consumption and lower CO 2 methanization rate.
  • the catalyst used for the methanation contains Ru, Pt, Rh, Pd or Ni on an alumina carrier.
  • WO 97/43207 describes the combination of a first stage for selective oxidation with a subsequent methanization stage with rhodium as the active component. With this combination, both processes can be operated under optimal conditions.
  • EP-A-1246286 which includes a methanation reactor of a selective oxidation unit as a final process step of gas purification, for ease of construction and handling, employ conventional catalysts, predominantly ruthenium or nickel based.
  • JP-A-2002/068707 deals with methanation catalysts supported on a refractory inorganic oxide selected from oxides of aluminum, titanium, silicon or zirconium.
  • EP-A-1707261 describes a process for the selective oxidation of CO with a catalyst containing ruthenium on a support of mixed metal oxides doped with lanthanides.
  • US Pat. No. 7,560,496 describes a process for the selective methanization of CO in the presence of CO.sub.2 using a catalyst comprising ruthenium, rhodium, nickel and / or cobalt as active component and at least one further dopant selected from the group consisting of iron, niobium, manganese, Molybdenum and zirconium on a carbon-based support material.
  • WO 2008/101875 relates to a catalytically active composition for the selective methanization of carbon monoxide in hydrogen- and carbon dioxide-containing streams, which is characterized in that it contains ruthenium as the active component and a lanthanum-cerium-zirconium oxide as the carrier material.
  • US-A-2005/009621 1 describes the selective methanization on a catalyst of Ru, Rh, Ni or combinations on ⁇ -zeolite, mordenite and faujasite. Although this achieves the desired CO concentrations below 100 ppm, the selectivity at temperatures above 190 ° C. at which the catalyst exhibits its activity drops markedly below 50%. Since the hydrogenation of CO2 per mole of 3/2 times as much hydrogen destroyed as the hydrogenation of CO, the demand for the highest possible selectivity is very important. In addition, a reasonable catalytic activity is achieved only over the very small temperature window between 170 ° C and 180 ° C.
  • the object of the invention was therefore to provide a catalyst for selective CO methanation which obtains its selectivity and activity in a broad temperature range.
  • a catalytically active composition which comprises ruthenium, rhodium, nickel, or cobalt or mixtures thereof as active component and rhenium as doping element contains a suitable carrier material.
  • a catalyst containing ruthenium, rhodium, nickel or cobalt or mixtures thereof as active component and rhenium as doping element on a suitable support material is capable of methanating CO in a broad temperature range of about 100 to ensure 300 ° C in a nearly constant selectivity over a long period of time.
  • Conventional catalysts show a significant drop in selectivity as the temperature and longer run times increase.
  • a significantly lower control effort is required because the temperature window in the methanation of the CO must be kept less accurate.
  • the invention thus provides a catalytically active composition for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams, containing as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt and as a dopant rhenium on a support material.
  • the catalytically active composition contains as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt, preferably ruthenium.
  • the active component is preferably present in the catalyst as an oxide.
  • the actual active mass is then generated by activation with hydrogen in situ.
  • An ex situ prereduction with eg hydrogen, forming gas or another suitable reducing agent is also possible.
  • the active component of the catalyst is in metallic form. The catalyst can then be incorporated both in this form and after a subsequent surface passivation of the metallic component in the reactor.
  • Suitable support materials are, according to the invention, all materials which can usually be used for this purpose in catalyst chemistry and which have a sufficiently high BET surface area and a corresponding porosity (pore volume).
  • Examples include carrier materials selected from the group consisting of Al2O3, ZrÜ2, T1O2, SiC, ZnO, oxides of Group IIA metals, oxides of groups HIB, IVB, VB, VIB transition metals, oxides of rare earth metals, aluminosilicates, zeolites , MOFs (Metal Organic Framework) and their mixtures.
  • Preferred supports according to the invention are those materials selected from the group consisting of Al 2 O 3, ZrO 2, T 2 O 2, and oxides of rare earth metals.
  • a particularly preferred carrier material according to the invention is a lanthanum-cerium-zirconium oxide (LaCeZr oxide) having a lanthanum oxide content of from 0.1 to 15% by weight, preferably from 1 to 10% by weight and more preferably from 3 to 7% by weight .-% used.
  • the cerium oxide content is 0.1 to 20 wt .-%, preferably 1 to 17 wt .-% and particularly preferably from 10 to 16 wt .-%, each based on the weight of the total support material.
  • the zirconium oxide content of the support material is advantageously from 30 to 99.8 wt .-%.
  • the carrier used according to the invention is characterized in that its physicochemical properties such as BET surface area, pore volume and lateral compressive strength have preferred values.
  • the BET surface area of the support materials used for the catalysts according to the invention is at least 10 m 2 / g, advantageously at least 20 m 2 / g, preferably at least 40 m 2 / g, more preferably at least 60m 2 / g and all more preferably at least 80m 2 / g.
  • the BET surface area is determined by a method according to DIN 66131.
  • the pore volume of the carrier material is advantageously in the range from 0.05 to 1.5 cm 3 / g, preferably in the range from 0.1 to 1.0 cm 3 / g, particularly preferably in the range from 0.15 to 0.9 cm 3 / g, most preferably in the range of 0.17 to 0.7 cm 3 / g, in particular in Range of 0.2 to 0.6 cm 3 / g.
  • the pore volume is determined by the method of mercury porosimetry according to DIN 66133.
  • their compressive strength is advantageously at least 0.2 kgf, preferably at least 0.5 kgf, more preferably at least 1.0 kgf, most preferably at least 1.5 kgf, in particular at least 2.0 kgf.
  • Side crush strength is a measure of the stability of a material when it exerts pressure on its side surfaces. The material is clamped between two punches (pre-load 0.5 N), which then move with 1, 6 mm / min test speed to each other and crush the material. The force needed to crush the material is recorded. Data result from a statistical evaluation of at least 20 moldings.
  • the support material used according to the invention may contain, in addition to the components mentioned, further materials which can usually be used for this purpose in catalyst chemistry, for example alumina.
  • Suitable binder materials are those which have a sufficiently high BET surface area.
  • the BET surface area of these additionally used binder materials should be at least 120 m 2 / g.
  • the content of these binder materials should not be 70% by weight, preferably 50% by weight, more preferably 30% by weight, and very particularly preferably 20% by weight, based in each case on the weight of the total support material exceed.
  • the loading of the support material with at least one of the abovementioned active components according to the invention is 0.1 to 20% by weight, preferably 0.2 to 10% by weight, more preferably 0.3 to 5% by weight, very particularly preferably 0.4 to 4.5 wt .-%, in particular 0.5 to 3 wt .-%. Further advantageous quantitative ranges are, for example, 0.1 to 10% by weight, 0.5 to 5% by weight and 0.7 to 4 and 1 to 3% by weight. The data are in each case based on the total weight of the catalytically active composition.
  • the loading of the support material with rhenium as doping element is 0.01 to 20% by weight, preferably 0.05 to 10 wt .-%, particularly preferably 0.07 to 5 wt .-%, most preferably 0.08 to 4 Wt .-%, in particular 0.1 to 3 wt .-%.
  • the data are in each case based on the total weight of the catalytically active composition.
  • a preferred composition of the catalytically active system according to the invention contains 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-% rhenium and 0.1 to 20 wt.
  • ruthenium based on the total weight of the catalytically active composition on a support selected from the group consisting of Al2O3, ZrÜ2, T1O2 and metal oxides of the rare earths, preferably on a support of ZrÜ2.
  • Another preferred composition of the catalytically active system according to the invention contains 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-% rhenium and 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.3 to 5 wt .-% of ruthenium, based on the total weight of the catalytically active composition on a support selected from the group consisting of zeolite A. , ⁇ -zeolite, mordenite, faujasite, ZSM-5 and MOF.
  • Another preferred composition of the catalytically active system comprises on a lanthanum-cerium-zirconia support having a lanthana content of 0.1 to 15% by weight and a ceria content of 0.1 to 20% by weight, respectively based on the weight of the total support material, 0.01 to 20 wt .-% rhenium and 0.1 to 20 wt .-% ruthenium, based on the total weight of the catalytically active composition.
  • a further preferred composition of the catalytically active system comprises on a lanthanum-cerium-zirconium oxide support with a lanthanum oxide content of 0.1 to 15 wt.% And a cerium oxide content of 0.1 to 20 wt. , in each case based on the weight of the total support material, 0.05 to 10 wt .-% rhenium and 0.5 to 5 wt .-% ruthenium, based on the total weight of the catalytically active composition.
  • Another preferred composition of the catalytically active system comprises on a lanthanum-cerium zirconia support having a lanthana content of 0.1 to 10% by weight and a ceria content of 0.1 to 7% by weight, respectively Based on the weight of the total support material, 0.07 to 5 wt .-% rhenium and 0.7 to 4 wt .-% ruthenium, based on the total weight of the catalytically active composition.
  • a particularly preferred composition of the catalytically active system comprises on a lanthanum-cerium zirconia support having a lanthanum oxide content of 3 to 7 wt .-% and a ceria content of 10 to 16 wt .-%, each by weight of the total support material, 0.08 to 4 wt .-% rhenium and 1 to 3 wt .-% ruthenium, based on the total weight of the catalytically active composition.
  • the catalyst according to the invention is characterized in that its physicochemical properties such as the phase composition by XRD, BET surface area, pore volume and lateral compressive strength have preferred values.
  • the catalyst of the invention is characterized in that the recorded in 2 ⁇ (2 theta) range from 5 ° to 80 ° XRD diffraction at least the diffraction peaks at 26.54 ° 2 ⁇ (2 theta), 28.12 ° 2 ⁇ (2 theta), 29.90 ° 2 ⁇ (2 theta), 34.55 ° 2 ⁇ (2 theta), 49.70 ° 2 ⁇ (2 theta), 53.90 ° 2 ⁇ (2 theta), 59.12 ° 2 ⁇ (2 theta), 61, 96 ° 2 ⁇ (2 theta), 66.42 ° 2 ⁇ (2 theta), 73.48 ° 2 ⁇ (2 theta).
  • the XRD analyzes were performed on a Bruker / AXS D8 Advance Series 2 using CuK alpha source (with a wavelength of 0.154 nm at 40 kV and 40 mA) and ⁇ - ⁇ geometry (Bragg-Brentano geometry). performed in reflection mode. The measurements were made over the measuring range: 5-80 ° (2 theta), 0.02 ° increments at 3.6 seconds / step.
  • the catalyst according to the invention is characterized in that its BET surface area is at least 10 m 2 / g, advantageously at least 20 m 2 / g, preferably at least 40 m 2 / g, particularly preferably at least 60m 2 / g and most preferably at least 80m 2 / g.
  • the BET surface area was determined according to DIN 66131.
  • the catalyst according to the invention is characterized in that its pore volume advantageously in the range of 0.05 to 1, 5 cm 3 / g, preferably in the range of 0.1 to 1, 0 cm 3 / g, particularly preferably in Range of 0.15 to 0.9 cm 3 / g, most preferably in the range of 0.17 to 0.7 cm 3 / g, in particular in the range of 0.2 to 0.6 cm 3 / g.
  • the method of mercury porosimetry according to DIN standard 66133 was used.
  • the catalyst according to the invention is in the form of shaped articles (such as tablets, extrudates, spherical particles, etc.), the compressive strength of the shaped articles advantageously being at least 0.2 kgf, preferably at least 0.5 kgf, particularly preferably at least 1, 0 kgf, most preferably at least 1, 5 kgf, in particular at least 2.0 kgf.
  • the lateral compressive strength is a measure of the stability of a material when it exerts pressure on its side surfaces. The material is clamped between two punches (pre-load 0.5 N), which then move with 1, 6 mm / min test speed to each other and crush the material. The force needed to crush the material is recorded. Data result from a statistical evaluation of at least 20 molded articles.
  • the preparation of the catalyst used according to the invention is carried out in the usual manner, for example by the active component and optionally the doping element, preferably in the form of their salts / hydrates, brought into solution and then applied in a suitable manner, for example by impregnation on the support become. Thereafter, the catalyst is dried, calcined, optionally reduced and optionally passivated.
  • 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. Implementation and process conditions are described, for example, in the Handbook of Heterogenous Catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, pages 57 to 66 and 147 to 149.
  • An alternative method of preparation involves the kneading of the support materials with the salts / hydrates of the active and optionally doping elements with subsequent extrusion, drying and optionally calcination, optionally reduction and optionally passivation.
  • the kneading of the carrier material with the active compounds and the further working steps can be carried out in the usual manner with known apparatuses.
  • moldings from pulverulent raw materials can be carried out by customary methods known to the person skilled in the art, for example tableting, aggregation or extrusion, as described i.a. in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pages 414-417.
  • auxiliaries known to the person skilled in the art such as binders, lubricants and / or solvents, may be added.
  • the invention also provides the use of a catalytically active composition for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams, which is characterized in that it comprises as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and Cobalt, preferably ruthenium and as a dopant rhenium on a support material selected from the group consisting of Al2O3, ZrÜ2, T1O2, SiC, ZnO, oxides of Group IIA metals, oxides of groups HIB, IVB, VB, VIB transition metals, oxides of metals rare earths, aluminosilicates, zeolites, MOFs (Metal Organic Framework) and mixtures thereof.
  • ruthenium, rhodium, nickel and Cobalt preferably ruthenium and as a dopant rhenium on a support material selected from the group consisting of Al2O3, ZrÜ2, T1O2, SiC, Zn
  • a preferred embodiment of the use according to the invention of the catalytically active composition for the selective methanization of carbon monoxide in hydrogen- and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which comprises as active component at least one element selected from the group consisting of Ruthenium, rhodium, nickel and cobalt, preferably ruthenium and containing rhenium as a dopant on a support material, wherein the total loading of the carrier material with the active component 0.1 to 20 wt .-% and with rhenium 0.01 to 20 wt .-%, each based on the total weight of the catalytically active composition, and the carrier material one or more components selected from the group consisting of Al 2 O 3, Zr 2 O, T 1 O 2, SiC, ZnO, Group IIA metals, Group HIB, IVB, VB, VIB transition metals, rare earth metal oxides, aluminosilicates, zeolites, MOFs (Metal
  • a particularly preferred embodiment of the use according to the invention of the catalytically active composition for the selective methanation of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which comprises at least one element selected from the group as the active component of ruthenium, rhodium, nickel and cobalt, preferably ruthenium, and containing rhenium on a carrier material as doping agent, the total loading of the carrier material with the active component being 0.1 to 20% by weight, preferably 0.2 to 10% by weight.
  • the support material preferably a component selected from the group consisting of zeolite A, ß-zeolite, Mordenite, faujasite, ZSM-5 and MOF.
  • a catalytically active composition which comprises as active component at least one element selected from the group consisting of Ruthenium, rhodium, nickel and cobalt, preferably ruthenium and contains as a dopant rhenium on a support material, wherein the total loading of the support material with the active component 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.3 to 5 wt .-% and with rhenium 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-%, each based on the total weight of the catalytically active composition, and the support material preferably contains a lanthanum-cerium-zirconium oxide, wherein the support material
  • the invention likewise provides a process for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams, characterized in that a catalytically active composition is used which comprises as active component at least one element selected from the group consisting of ruthenium, rhodium, Nickel and cobalt, preferably ruthenium and as a dopant rhenium on a support material selected from the group consisting of Al 2 O 3, ZrO 2, TIO 2, SiC, ZnO, Group IIA metals, Group HIB, IVB, VB, VIB oxides, transition metals, rare earth metal oxides, aluminosilicates, zeolites, MOFs (Metal Organic Framework) and mixtures thereof.
  • a catalytically active composition which comprises as active component at least one element selected from the group consisting of ruthenium, rhodium, Nickel and cobalt, preferably ruthenium and as a dopant rhenium on a support material selected from the group consist
  • a preferred embodiment of the process according to the invention for the selective methanization of carbon monoxide in hydrogen- and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which contains as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt, preferably ruthenium and contains as a dopant rhenium on a support material, wherein the total loading of the support material with the active component 0.1 to 20 wt .-%, and with rhenium 0.01 to 20 wt .-%, each based on the total weight of the catalytically active composition, and the support material is one or more components selected from the group consisting of Al 2 O 3 , ZrO 2 , TiO 2 , SiC, ZnO, oxides of Group IIA metals, oxides of groups HIB, IVB, VB , VIB transition metals, oxides of rare earth metals, aluminosilicates, zeolites
  • a particularly preferred embodiment of the process according to the invention for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which contains as active component at least one element selected from the group consisting of ruthenium, rhodium, Nickel and cobalt, preferably ruthenium, and containing rhenium on a carrier material as doping agent, the total loading of the carrier material with the active component being 0.1 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 0, 3 to 5 wt .-% and with rhenium 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-%, each based on the total weight of the catalytic active compound, and the support material preferably contains a component selected from the group consisting of zeolite A, ⁇ -zeolite, mordenite, faujasite, ZSM-5 and MOF
  • a catalytically active composition which contains at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt as the active component , preferably ruthenium and contains as a dopant rhenium on a support material, wherein the total loading of the support material with the active component 0.1 to 20 wt .-%, preferably 0.2 to 10% by weight, particularly preferably 0.3 to 5 wt.
  • the support material preferably contains a lanthanum-cerium-zirconium oxide, wherein the support material comprises a lanthanum oxide Content of 0.1 to 15 wt .-%, a cerium oxide content of 0.1 to 20 wt .-% and a zirconium oxide content of 30 to 99.8 wt .-%, based on the weight of the total Carrier materials, contains.
  • the selective methanation process according to the invention can be carried out in a temperature range of preferably 100 to 300 ° C.
  • Particularly advantageous is the selective methanization of CO in a temperature range of 180 to 260 ° C.
  • This temperature allows for direct thermal integration to the upstream cryogenic conversion. It is thus possible to couple the methanation stage according to the invention directly to the low-temperature conversion stage.
  • the high activity with equally high CO selectivity in this temperature range ensures that a stable and above all thermally integrated operation of the catalyst becomes possible.
  • the inventive method is operated in a mode of operation, the GHSV in a range of 200 to 20,000 r 1 , preferably in a range of 500 to
  • the GHSV "gas hourly space velocity" is an indication of the gas flow of a reaction gas in liters per liter of catalyst and per hour at standard temperature and pressure.
  • the novel process for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing streams on the highly active methanation catalyst according to the invention is carried out in customary apparatuses and under customary conditions for carrying out a methanation reaction, as described, for example, in the Handbook of heterogeneous catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, page 353, and with overflow of the catalyst with a CO and hydrogen-containing process gas.
  • the process gas suitable for the methanation process is a synthesis gas that can be generated by reforming solid, liquid and gaseous fuels.
  • Preferred fuels include natural gas, LPG, long-chain hydrocarbons (gasoline, diesel) and alcohols such as methanol or ethanol.
  • Reforming means the processes known to the person skilled in the art, such as steam reforming, partial oxidation and autothermal reforming.
  • Preferred reforming processes include steam reforming and autothermal reforming of hydrocarbons such as natural gas, gasoline and diesel.
  • the catalytically active composition is thus outstandingly suitable for CO fine cleaning in hydrogen and carbon dioxide-containing reformate streams, in particular for use in the production of hydrogen for fuel cell applications.
  • the invention will be explained in more detail with reference to the following embodiments, but without thereby making a corresponding limitation.
  • the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReG-4) and dried again at 120 ° C. for sixteen hours.
  • the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 2% by weight of Re as a dopant.
  • the BET surface area of the finished catalyst was 83 m 2 / g *) .
  • the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C for sixteen hours.
  • HReC perrhenic acid solution
  • the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 1 wt% Re as a dopant.
  • the BET surface area of the finished catalyst was 86 m 2 / g *) .
  • Example 3 148.1 g of a lanthanum-cerium-zirconium oxide support (containing 65% by weight of ZrO 2 , 15% by weight of CeO 2 , 5% by weight of La 2 C> 3 and 15% by weight of Al 2 O 3) were mixed with a 30% strength by weight RuC solution, the amount of which was adjusted so that the finished catalyst carried 2% by weight of Ru as the active composition. Subsequently, the impregnated support was dried in a rotary kiln at 120 ° C for sixteen hours and then calcined at 475 ° C for two hours (at a heating rate of 4 ° C / min).
  • the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C for sixteen hours.
  • HReC perrhenic acid solution
  • the concentration of perrhenic acid was adjusted so that the finished catalyst after drying contained 0.5 wt .-% Re as a dopant.
  • the BET surface area of the finished catalyst was 85 m 2 / g *) .
  • the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C for sixteen hours.
  • HReC perrhenic acid solution
  • the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 0.25 wt% Re as a dopant.
  • the BET surface area of the finished catalyst was 88 m 2 / g * >.
  • the ruthenium catalyst thus obtained was subsequently impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C. for sixteen hours.
  • HReC perrhenic acid solution
  • the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 0.1 wt% Re as a dopant.
  • the BET surface area of the finished catalyst was 86 m 2 / g *) . *)
  • the BET surface area of the respective catalysts according to the invention was determined according to DIN 66131.
  • Example 8 Selective methanation using the catalysts from Examples 1 to 7
  • the catalyst mixture consisted of about 20 ml catalyst pellets (1, 5 x 1, 5 mm).
  • the feed used was 5 ml of stea- tite spheres with a diameter of 1.8 to 2.2 mm, which filled the residual volume of the reactor.
  • the catalyst was first reduced with 90 l / h of nitrogen and 10 l / h of hydrogen at 230 ° C for one hour.
  • the gas composition chosen for the experiment is typical for the output of the low-temperature shift stage after the reforming of methane and was 22% by volume H 2 , 28% by volume N 2 , 25% by volume H 2 O, 13% by volume. % CO 2 , 5% CO by volume and 0.5% CH 4 by volume. All experiments were carried out at a pressure of 2 bara and a load of 5000 lh- 1 -
  • the selectivity is the quotient of the amount of CO converted and the amount of methane produced (in% by volume).
  • the turnover refers to CO.
  • Example 1 2% by weight Ru / 2% by weight Re 83% 51%
  • Example 2 2% by weight Ru / 1% by weight Re 84% 53%
  • Example 3 2% by weight Ru / 0.5% by weight Re 82% 49%
  • Example 4 2% by weight Ru / 0.25% by weight Re 80% 45%
  • Example 5 2% by weight Ru / 0.1% by weight Re 82% 46%
  • Rhenium doped ruthenium catalysts from Examples 1 to 5 significantly higher CO selectivities over the temperature range of 200 to 260 ° C than the two rhenium-free catalysts from Comparative Examples 6 and 7.

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Abstract

La présente invention concerne une composition catalytiquement active pour la méthanisation sélective de monoxyde de carbone dans des flux de réformat contenant de l'hydrogène et du dioxyde de carbone, comprenant comme composants actifs au moins un élément sélectionné dans le groupe constitué de ruthénium, rhodium, nickel et cobalt, et comme agent de dopage du rhénium sur une matière support. Le catalyseur selon l'invention est utilisé, de préférence, pour la mise en oeuvre de réactions de méthanisation dans une plage de températures comprise entre 100 et 300°C aux fins d'utilisation dans la production d'hydrogène pour des applications de piles à combustible.
EP16714331.2A 2015-03-26 2016-03-23 Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone Pending EP3274088A1 (fr)

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PCT/EP2016/056418 WO2016151031A1 (fr) 2015-03-26 2016-03-23 Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone

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JP4864688B2 (ja) * 2006-12-25 2012-02-01 日揮触媒化成株式会社 一酸化炭素メタネーション用触媒および該触媒を用いた一酸化炭素のメタネーション方法
WO2008101875A1 (fr) 2007-02-23 2008-08-28 Basf Se Catalyseur et procédé de méthanisation sélective de monoxyde de carbone
KR20090119766A (ko) * 2007-03-13 2009-11-19 우미코레 아게 운트 코 카게 일산화탄소의 메탄화를 위한 촉매로서 금속 도핑된 니켈 산화물
CN102151570A (zh) * 2011-03-01 2011-08-17 上海中科高等研究院 一种甲烷-二氧化碳重整反应催化剂及其制备方法

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EP3072589A1 (fr) 2016-09-28
US20180085739A1 (en) 2018-03-29
JP6808638B2 (ja) 2021-01-06
JP2018514372A (ja) 2018-06-07
CN107427819A (zh) 2017-12-01
CN107427819B (zh) 2021-08-24
CA2980254C (fr) 2023-07-25
US10780422B2 (en) 2020-09-22
CA2980254A1 (fr) 2016-09-29
KR20170130561A (ko) 2017-11-28
WO2016151031A1 (fr) 2016-09-29

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