WO2018219986A1 - Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant de l'iridium et/ou du rhodium - Google Patents

Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant de l'iridium et/ou du rhodium Download PDF

Info

Publication number
WO2018219986A1
WO2018219986A1 PCT/EP2018/064142 EP2018064142W WO2018219986A1 WO 2018219986 A1 WO2018219986 A1 WO 2018219986A1 EP 2018064142 W EP2018064142 W EP 2018064142W WO 2018219986 A1 WO2018219986 A1 WO 2018219986A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
catalyst
iridium
rhodium
carbon dioxide
Prior art date
Application number
PCT/EP2018/064142
Other languages
German (de)
English (en)
Inventor
Stephan A Schunk
Carlos LIZANDARA
Guido WASSERSCHAFF
Robert Mueller
Andrian Milanov
Marcelo Daniel Kaufman Rechulski
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 WO2018219986A1 publication Critical patent/WO2018219986A1/fr

Links

Classifications

    • 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
    • C01B32/40—Carbon monoxide
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/42—Platinum
    • 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
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—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
    • B01J23/83—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 rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—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
    • 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
    • C01B3/06—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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • 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
    • C01B2203/1082—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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P20/141—Feedstock
    • 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 a process for the hydrogenation of carbon dioxide, which is characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst comprising an iridium- and / or rhodium-containing active material.
  • a catalyst comprising an iridium- and / or rhodium-containing active material.
  • RWGS reverse water gas shift
  • JP 3328847 B2 describes the use of rhodium-containing catalysts for the methanation, i. Hydrogenation of carbon dioxide with hydrogen to methane, described at temperatures of 200 to 550 ° C.
  • WO 2015/091310 A1 discloses the use of iridium-containing catalysts for the dry reforming of mixtures of hydrocarbons and carbon dioxide to synthesis gas.
  • Synthesis gas is to be understood as meaning a gas mixture containing hydrogen and carbon monoxide, which can be used as a basic chemical in a large number of industrial processes. Depending on their use, synthesis gases have different ratios of hydrogen to carbon monoxide.
  • C02 emissions in Germany in 2010 amounted to approx. 960 million t C02 equivalent, with the chemical industry contributing around 5%.
  • Suitable basic chemicals are, for example, hydrogen and synthesis gas. The latter forms the ideal interface to existing petrochemical processes for production of eg methanol, dimethyl ether or Fischer-Tropsch products.
  • the global demand for hydrogen and syngas is currently 50 million t / a, or 220 million t / a.
  • WO2015 / 135968 discloses catalysts based on Ni, Co, Zn, Fe mixed oxides.
  • noble metal-containing catalysts for the hydrogenation of carbon dioxide to carbon monoxide are described in US Pat. No. 8,961,829 B2.
  • a catalyst is disclosed in which platinum has been deposited on cerium, manganese and / or magnesium oxide. In the examples, a Pt loading of 0.3 wt .-% is given.
  • US 201 1/0105630 discloses platinum or palladium based catalysts for the hydrogenation of carbon dioxide to carbon monoxide.
  • Potential support materials include alumina, magnesia, silica, titania, optionally sulfated zirconia, tungsten zirconia, aluminum trifluoride, fluorinated alumina, bentonites, zeolites, carbon-based supports, molecular sieves, and combinations thereof.
  • the stated preferred loading is 10 to 20 wt .-%.
  • WO 2013/135710 discloses a carbon dioxide hydrogenation to carbon monoxide in a shell and tube reactor.
  • the catalyst disclosed are hexaaluminates having the following formula:
  • L Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu
  • M Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu, Ag and / or Au.
  • the method of preparation of these solid hexaaluminate catalysts involves a multi-step process involving the steps of precipitation, filtration, washing, drying, molding and calcining. Examples of carbon dioxide hydrogenation are not disclosed.
  • WO 2015/135968 discloses a process for preparing a catalyst for high temperature carbon dioxide hydrogenation to carbon monoxide.
  • the disclosed catalyst contains at least one crystalline material comprising yttrium and aluminum, wherein it is characteristic of the crystalline material that it has at least one of the following structures: cubic garnet structure, orthhombic perovskite structure, hexagonal perovskite structure and / or monoclinic perovskite structure (ie Y4AI209), wherein the catalyst contains Cu, Fe, Co, Zn and / or Ni.
  • the loading of the yttrium-containing material is 0.1 to 10 mol .-% indicate.
  • the examples show good performance in carbon dioxide hydrogenation, as well as low carbon deposition on the catalyst.
  • the experiments were carried out at a GHSV of 30,000 and 40,000 r 1 .
  • the method of preparation of these catalysts comprises a multistage process comprising the stages, precipitation, filtration, drying, pre-calcination, molding, post-
  • One of the objects underlying the invention is to provide a catalyst for carbon dioxide hydrogenation with high activity and stability, i. good resistance to coke buildup. Furthermore, the tendency to methanation should be low.
  • this catalyst is inexpensive to produce, i. a manufacturing method can be selected that includes as few process steps.
  • a supported catalyst can be prepared with the aid of the process steps impregnation, drying, calcination, whereby a period of typically V2 hours is estimated for impregnation on a laboratory scale.
  • a full-body catalyst requires the process steps of precipitation, filtration, washing, drying / calcination, molding and (post) calcination, with half a working day being estimated for a laboratory scale precipitation.
  • the active metal loading should be as low as possible to be energy efficient and resource efficient.
  • a further object is also that the process according to the invention is suitable for the carbon dioxide hydrogenation to carbon monoxide in the presence of hydrocarbons, in particular methane, i. that methane present in the educt gas mixture is reformed.
  • Another object within the scope of the invention is to identify particularly active catalysts which, even at high loads, in particular greater than 10,000 h-1, are still able to convert a reactant gas mixture into a composition close to the thermodynamically predicted equilibrium lies.
  • Particularly active catalysts make it possible to make the reactor smaller and thus keep the investment for this part of the plant small.
  • high temperature process is meant processes at temperatures of> 600 ° C, in particular> 600 ° C and ⁇ 1400 ° C.
  • the invention relates to a process for carbon dioxide hydrogenation, which is characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst comprises a support material and an active composition, wherein as support materials Ce, La, Zr, Al, Ti, Ca, Si, Mg oxides, SiC, MgAI spinels, Sr aluminates, La , Ba, Sr-hexa-aluminates and / or mixtures thereof, and the active composition contains at least iridium and / or rhodium as active component, wherein the content of iridium (calculated as metal) with respect to the total weight of the catalyst is in a range of 0.005 to 2 wt .-% and the content of rhodium (calculated as metal) relative to the total weight of the catalyst in a range of 0.005 to ⁇ 1 wt .-% and the temperature of the educt gases, carbon dioxide with Hydrogen, when contacted with the active composition in the range of 600 to 1
  • Carbon dioxide is preferably reacted with hydrogen in the presence of a catalyst to give carbon monoxide and water.
  • the content of rhodium in relation to the total weight of the catalyst is in a range of preferably 0.005 to 0.75 wt.%, More preferably 0.01 to 0.75 wt.%, In particular 0.025 to 0, 75% by weight.
  • the content of iridium is in a range of preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight, more preferably 0.01 to ⁇ 1% by weight, based on the total weight of the catalyst .-%, more preferably 0.01 to 0.75 wt .-%, in particular 0.025 to 0.75 wt .-%. All mixtures of iridium and rhodium known to the person skilled in the art are conceivable. Particularly preferred is iridium.
  • the total content of a mixture of iridium and rhodium in relation to the total weight of the catalyst is in a range of preferably 0.005 to 2% by weight, preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight %, more preferably 0.01 to ⁇ 1 wt .-%, more preferably 0.01 to 0.75 wt .-%, in particular 0.025 to 0.75 wt .-%.
  • oxides As support materials, oxides, aluminates and carbides are preferred. Examples of oxides which may be mentioned as oxides are Ce, La, Zr, Al, Ti, Ca, Si, Mg oxides and mixtures thereof, carbides SiC and aluminates spinels, in particular MgAl spinels, Sr aluminates and La, Ba, Sr 2. Hexa-aluminates.
  • the following support materials are preferred: Ce, La, Zr, Al-oxides, Zr-hydroxides doped with La & Ce, Al 2 O 3 (delta-theta), SiC, Y on ZrO 2, Ce on ZrO 2, Ca-Si-ZrO 2, 35% MgO 65% Al 2 O 3, 80% MgO 20% Al 2 O 3, 37% CaO, 63% Al 2 O 3, ZrO 2 (monoclinic), ZrO 2 (tetragonal), 44.6% CaO 54.9% ZnO, TiO 2, MgO, SrAl 2 O 4, BaAl 2 O 4, La 2 Zr 2 O 7.
  • the content of doping elements is advantageously in the range from 0 to 5 wt .-%, in particular 1 to 3 wt .-%, with respect to the carrier material.
  • the zirconium dioxide-containing active composition has a specific surface area of> 5 m 2 / g, preferably> 20 m 2 / g, more preferably> 50 m 2 / g and in particular> 80 m 2 / g.
  • the determination of specific surface area of the catalyst was achieved by gas adsorption by the BET method (ISO 9277: 1995).
  • the iridium and / or rhodium it is particularly advantageous for the iridium and / or rhodium to be present in finely divided form on the carrier, in particular zirconium dioxide carrier, since this achieves high catalytic activity with a low content of Ir and / or Rh.
  • the iridium-containing and / or rhodium-containing particles have a size ⁇ 50 nm, preferably ⁇ 30 nm, preferably ⁇ 20 nm and more preferably ⁇ 10 nm.
  • the iridium-containing and / or rhodium-containing particles have a size in the range from 1 to 100 nm, preferably in the range from 5 to 50 nm.
  • the iridium and / or rhodium is homogeneously on the carrier or in the active mass.
  • the iridium and / or rhodium is particularly preferably present in homogeneous and finely divided form on the carrier or in the active composition.
  • the catalyst used according to the invention is characterized in that the Ir and / or Rh on a carrier, advantageously a zirkoni umdioxid Anlagenn carrier, is present and this doped with further elements.
  • a carrier advantageously a zirkoni umdioxid ambiencen carrier
  • elements from the group of rare earths ie from the group Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
  • the catalyst also contains one or more doping elements in addition to the iridium and / or rhodium and optionally zirconium dioxide, then the proportion by weight of doping elements, in particular rare earth doping elements, based on the total weight of the catalyst is in the range from 0.01 to 80 Wt .-%, preferably in the range of 0.1 to 50 wt .-% and particularly preferably in the range of 1, 0 to 30 wt .-%.
  • the catalyst used according to the invention is characterized in that it contains iridium and / or rhodium and a support material, advantageously zirconium dioxide, yttrium as a further doping element, wherein the yttrium is present in oxidic form.
  • a support material advantageously zirconium dioxide, yttrium as a further doping element, wherein the yttrium is present in oxidic form.
  • the yttria content based on the total weight of the catalyst, in the range of 0.01 to 80 wt .-%, preferably from 0.1 to 50 wt .-% and more preferably from 1, 0 to 30 wt .-% ,
  • the catalyst used according to the invention is characterized in that, in addition to iridium and / or rhodium and a support material, preferably zirconium dioxide, additionally contains one or more, preferably two, elements from the group of rare earths as doping elements.
  • the content is preferably to doping elements with respect to the total weight of the catalyst, in the range of 0.01-80 wt.%, preferably 0.1-50 wt.%, and more preferably 1-30 wt.%. Particular preference is given to using lanthanum (La) and cerium (Ce) as doping elements.
  • catalysts used according to the invention which comprise Ir / ZrO 2 and / or Rh / ZrC 2 active compositions in which the zirconium dioxide has a doping with yttrium and / or a doping with lanthanum and / or cerium.
  • the active compounds used according to the invention which are used for the process according to the invention also contain promoters and / or further metal cations, which further increase the efficiency of the catalysts.
  • doping elements may include, but are not limited to: noble metal promoters, non-noble metal promoters, and other metal cations:
  • the catalyst used according to the invention or the active composition contains at least one noble metal-containing promoter from the group Pt, Pd, Ru, Au, where the proportion of noble metal-containing promoters in relation to the total weight of the catalyst is 0.01. 5 wt .-% and more preferably in the range of 0.1 to 3 wt .-% have.
  • the catalyst used according to the invention comprises at least one non-noble metal-containing promoter from the group Ni, Co, Fe, Mn, Mo, W, the fraction of non-noble metal-containing promoters being in the range from 0.1 to 50 based on the total weight of the catalyst Wt .-%, preferably in the range of 0.5 to 30 wt .-% and more preferably in the range 1-20 wt .-% is.
  • the catalyst used according to the invention also comprises a proportion of further metal cations, which are preferably selected from the group Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn, with Ca and / or Mg being particularly preferred.
  • the components present in the catalyst used in the present invention i. the said noble metals, alkaline earth metals, doping elements, promoters and support materials can be present in elemental and / or oxidic form.
  • examples being impregnation with impregnating solution, impregnation with pore volume, spraying of the impregnating solution, washcoating and precipitation powdery raw materials can be carried out by methods known to those skilled in the art, such as tableting, aggregation or extrusion, as described, inter alia, in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp. 414-417.
  • the iridium-containing and / or rhodium-containing active composition may also be applied to a carrier, monolith or honeycomb body.
  • the monolith or honeycomb body may be made of metal or ceramic.
  • the molding of the active composition or the application of the active composition on a carrier or carrier bodies is of great industrial significance for the fields of application of the catalyst used according to the invention.
  • the shape of the particles affect the pressure drop caused by the fixed catalyst bed. Impression may be carried out by any method known to those skilled in the art of catalyst preparation (see, eg, Deutschmann, O., Knözinger, H., Kochloefl, K. and Turek, T. 201. 1. Heterogeneous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts, Ullmann's Encyclopedia of Industrial Chemistry).
  • the present invention further relates to a catalytic process for the carbon dioxide hydrogenation to carbon monoxide, i. for the production of synthesis gas, characterized in that:
  • the pressure of the reactant gas in contacting with the catalyst is in the range of 1 to 100 bar a bs and the temperature of the educt gas in contacting with the catalyst is in the range of 20 to 1400 ° C,
  • the GHSV of the process has a value in the range of 1,000 to 1,000,000 r 1 ,
  • the synthesis gas produced has a H 2 / CO ratio in the range of 0.1 to 10, more preferably in the range of 1 to 4, and most preferably in the range of 1, 5 to 3.
  • the molar ratio of educt gas H2 / CO 2 in the range from 0.1 to 20, preferably from 0.3 to 10, more preferably from 1 to 7, in particular from 2 to 5, is advantageous.
  • the educt gas has the following composition:
  • the molar fraction of CO 2 is advantageously in the range from 1 to 90%, preferably from 3 to 75%, more preferably from 10 to 60%, in particular from 20 to 50%.
  • the molar fraction of H 2 is advantageously in the range from 1 to 99%, preferably from 10 to 90%, more preferably from 20 to 85%, in particular from 40 to 80%.
  • the molar fraction of CH4 is advantageously in the range from 0 to 30%, preferably from 0 to 20%, more preferably 0 to 15%, more preferably 0 to 10%, in particular from 0 to 5%.
  • the molar fraction of N 2 is advantageously in the range from 0 to 80%, preferably from 0 to 20%, in particular from 0 to 5%.
  • the molar fraction of O 2 is advantageously in the range from 0 to 5%, preferably from 0 to 2%, more preferably from 0 to 1%, in particular from 0 to 0.5%.
  • the molar fraction of H 2 O is advantageously in the range from 0 to 99%, preferably from 0 to 90%, more preferably from 0 to 40%, more preferably 0 to 20%, further preferably 0 to 15%, further preferably 0 to 10%, in particular 0 to 5%.
  • the pressure of the educt gas when contacting with the catalyst is advantageously in the range from 3 to 60 bar a bs, in particular from 10 to 30 bar a bs.
  • the temperature of the educt gas when it comes into contact with the catalyst is in the range from 600 to 1300 ° C., preferably from 750 to 1200 ° C., in particular from 850 to 1200 ° C.
  • the GHSV of the process is in the range from 2000 to 700,000 hr.sup.- 1 , preferably from 5000 to 500,000 hr.sup.- 1 , in particular from 10,000 to 300,000 hr.sup.- 1 .
  • the process according to the invention can be advantageously used as an ATR process (autothermal reforming), such as, for example, in Reimert, et al. , 201 1. Gas Production, 2. Processes. Ullmann's Encyclopedia of Industrial Chemistry. described be performed.
  • ATR process oxygen is thus introduced in addition to the educt gas.
  • a characteristic of the process according to the invention for the hydrogenation of carbon dioxide, if appropriate in the presence of hydrocarbons, advantageously methane, and / or water, is that ZrO 2 -containing active compositions can be used which have a relatively low content of iridium and / or rhodium and nevertheless one have high catalytic efficiency.
  • active compositions which, for example, have only 1% by weight or less than 1% by weight of iridium and / or rhodium.
  • the process according to the invention can be carried out with a reactant fluid which has small amounts of water vapor.
  • the water vapor / carbon dioxide content in the educt gas is less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05.
  • the iridium-containing and / or rhodium-containing active component is exposed to a strong physical and chemical load, since the process is carried out at a temperature in the range of 600 to 1300 "C, the process pressure in the range of 5 to 500 bar , preferably in the range of 10 to 250 bar, and more preferably in the range of 20 to 100.
  • the coke deposit is ⁇ 2 wt .-% carbon content with respect to the catalyst used, more preferably ⁇ 1 wt .-%, more preferably ⁇ 0.5 wt .-%, in particular ⁇ 0.2 wt .-%. Due to the very high thermal stability and the operational stability under pressure at pressures of 5 to 40 bar of the catalyst this can be used over long process times, several thousand hours away.
  • the corresponding amount of Sr (N 0.3) 2 (4.344 g with a purity of 99.7% by weight) was dissolved in 250 ml DI water with stirring in a 500 ml beaker.
  • a dispersion of the AI source (15.462 g Disperal with 42.51 wt% AI) was added to this solution, whereupon a suspension has formed. This suspension was stirred for 30 minutes for homogenization.
  • the suspension was flash frozen dropwise in liquid nitrogen. The frozen droplets were freeze-dried at -10 C and 2.56 mbar.
  • the freeze-dried powder was calcined in air to decompose the nitrates and chlorides.
  • the heating rate was 1 K / min.
  • the sample was heated to 150 C, 250 C and 350 C with a residence time of 1 hour at the temperature reached.
  • the final calcination temperature was 450 C and the residence time was again 1 hour, then cooled to ambient temperature.
  • the precalcined sample was subjected to a molding process. 3% by weight of graphite was added to the sample and mixed thoroughly. The mixture was pelletized with a Korsch XP1 pelletizer in automatic mode. The direction finding tool had a diameter of 13 mm and the applied force for picking up pellets with a height of 2 mm was 40 kN. The pellets were crushed and sieved to 315-500 pm.
  • the crushed and sieved sample (315-500 pm) was subjected to final calcination in air to remove the graphite and to form the desired hexaaluminate phase.
  • the final calcination temperature was 1400 C with a heating rate of 5 K / min and a residence time of 2 hours.
  • W015135968 Catalyst S2 was prepared as described in WO 15/135968 A1.
  • the catalysts S3 and S4 were prepared analogously to the prior art, US 201 1/0105630, via impregnation process:
  • the dried sample was calcined in air (6 l / min) in an oven (Nabertherm TH120 / 12) as follows: heating rate of 1 K / min up to a temperature of 250 ° C, residence time of 1 h, heating rate of 5 K / min up to a temperature of 400 C, residence time of 4 h, then cool to ambient temperature.
  • the drying took place in a drying oven at 80 C for 16 hours.
  • the dried sample was calcined as follows under air (6 I / min) in a furnace (Nabertherm TH120 / 12): heating rate of 1 K / min up to a temperature of 250 0 C, residence time of 1 hour, heating rate of 5K / min up to a temperature of 400 0 C, residence time of 4h, then cool to ambient temperature.
  • Table III List of carrier materials used
  • Table IV List of impregnating solutions used Table V summarizes the catalysts used according to the invention.
  • Table V List of Ir and Rh catalysts used in the invention
  • the determination of the loss on ignition (LOI) is a crucial point in the production of impregnated catalysts with a well-defined metal loading.
  • the carrier used had an LOI of 2.43%.
  • the impregnation was carried out as 100% incipient wetness impregnation (100% ICW) (moistening impregnation) using a solution of DI water with a 0.199 molar IrC solution.
  • Table 2 Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in educt gas) of the catalysts S1-S4 (prior art), E1-E6 (according to the invention) of the phase I - VI of the table 1
  • the catalysts used in the invention show a comparable performance as the full catalysts S1 and S2 from the prior art. Furthermore, the performance is stable over all phases.
  • the activity of prior art catalysts S3 and S4 decreases from phase V and phase VI, respectively; Furthermore, the conversion of H2 in phases I and II, in which no methane is added, worse than S1 and S2 and E1 -E6.
  • Table 3 Carbon deposition from the catalysts after the screening according to Table 5 (indicator of stability)
  • Table 7 Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in educt gas) of the catalysts E4 (0.5% by weight Ir), E5 (0.05% by weight Ir) and E7 ( 0.1% by weight Ir) of phase I-XI II of Table 6

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé d'hydrogénation de dioxyde de carbone, caractérisé en ce qu'il consiste à faire réagir du dioxyde de carbone avec de l'hydrogène en présence d'un catalyseur qui contient une matière active à base d'iridium et/ou de rhodium.
PCT/EP2018/064142 2017-06-02 2018-05-30 Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant de l'iridium et/ou du rhodium WO2018219986A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17174175 2017-06-02
EP17174175.4 2017-06-02

Publications (1)

Publication Number Publication Date
WO2018219986A1 true WO2018219986A1 (fr) 2018-12-06

Family

ID=59152626

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/064142 WO2018219986A1 (fr) 2017-06-02 2018-05-30 Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant de l'iridium et/ou du rhodium

Country Status (2)

Country Link
TW (1) TW201902818A (fr)
WO (1) WO2018219986A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3328847B2 (ja) 1992-11-09 2002-09-30 株式会社日立製作所 水素化用触媒とその製造方法及び水素化方法
US20110105630A1 (en) 2009-11-04 2011-05-05 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Catalytic Support for use in Carbon Dioxide Hydrogenation Reactions
WO2013135710A2 (fr) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé pour la réalisation d'une réaction rwgs dans un réacteur à faisceau tubulaire
US8961829B2 (en) 2007-04-27 2015-02-24 Saudi Basic Industries Corporation Catalytic hyrogenation of carbon dioxide into syngas mixture
WO2015091310A1 (fr) 2013-12-20 2015-06-25 Basf Se Procédé de reformage de mélanges d'hydrocarbures et de dioxyde de carbone
WO2015135968A1 (fr) 2014-03-14 2015-09-17 Basf Se Catalyseur contenant de l'yttrium pour l'hydrogénation du dioxyde de carbone à haute température, l'hydrogénation du dioxyde de carbone à haute température et le reformage combinés et/ou le reformage ainsi qu'un procédé d'hydrogénation du dioxyde de carbone à haute température, d'hydrogénation du dioxyde de carbone à haute température et de reformage combinés et/ou de reformage
US20150336795A1 (en) * 2012-12-21 2015-11-26 Basf Se Parallel preparation of hydrogen, carbon monoxide and a carbon-comprising product

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3328847B2 (ja) 1992-11-09 2002-09-30 株式会社日立製作所 水素化用触媒とその製造方法及び水素化方法
US8961829B2 (en) 2007-04-27 2015-02-24 Saudi Basic Industries Corporation Catalytic hyrogenation of carbon dioxide into syngas mixture
US20110105630A1 (en) 2009-11-04 2011-05-05 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Catalytic Support for use in Carbon Dioxide Hydrogenation Reactions
WO2013135710A2 (fr) 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé pour la réalisation d'une réaction rwgs dans un réacteur à faisceau tubulaire
US20150336795A1 (en) * 2012-12-21 2015-11-26 Basf Se Parallel preparation of hydrogen, carbon monoxide and a carbon-comprising product
WO2015091310A1 (fr) 2013-12-20 2015-06-25 Basf Se Procédé de reformage de mélanges d'hydrocarbures et de dioxyde de carbone
US20160311684A1 (en) * 2013-12-20 2016-10-27 Basf Se Method for reforming mixtures of hydrocarbons and carbondioxide
WO2015135968A1 (fr) 2014-03-14 2015-09-17 Basf Se Catalyseur contenant de l'yttrium pour l'hydrogénation du dioxyde de carbone à haute température, l'hydrogénation du dioxyde de carbone à haute température et le reformage combinés et/ou le reformage ainsi qu'un procédé d'hydrogénation du dioxyde de carbone à haute température, d'hydrogénation du dioxyde de carbone à haute température et de reformage combinés et/ou de reformage

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Handbook of Heterogeneous Catalysis", vol. 1, 1997, VCH VERLAGSGESELLSCHAFT, pages: 414 - 417
A. BANSODE; A. URAKAWA, J. CATAL., vol. 309, 2014, pages 66 - 70
BOGDAN V I ET AL: "Reduction of carbon dioxide by hydrogen on metal-carbon catalysts under supercritical conditions", RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A, CHEMICAL SOCIETY, LONDON, GB, vol. 90, no. 12, 6 November 2016 (2016-11-06), pages 2352 - 2357, XP036092287, ISSN: 0036-0244, [retrieved on 20161106], DOI: 10.1134/S0036024416120050 *
DEUTSCHMANN, O.; KNÖZINGER, H.; KOCHLOEFL, K.; TUREK, T.: "Ullmann's Encyclopedia of Industrial Chemistry", 2011, article "Heterogeneous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts"
HABER ET AL.: "Manual of methods and procedures for catalyst characterization", PURE & APPL. CHEM., vol. 67, no. 8/9, 1995, pages 1257 - 1306
J. GRACIANI; K. MUDIYANSELAGE; F. XU; A.E. BABER; J. EVANS; S.D. SENANAYAKE; D.J. STACCHIOLA; P. LIU; J. HRBEK; J. FERNANDEZ SANZ, SCIENCE, vol. 345, 2014, pages 546 - 550
REIMERT ET AL.: "Ullmann's Encyclopedia of Industrial Chemistry", 2011, article "Gas Production, 2. Processes"

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide

Also Published As

Publication number Publication date
TW201902818A (zh) 2019-01-16

Similar Documents

Publication Publication Date Title
EP3116826B1 (fr) Catalysezr contenant de l'yttrium pour la hydrogenation de dioxid de carbone, hydrogenation de dioxid de carbone a haute temperature et/ou reformage et procede pour la hydrogenation de dioxid de carbone et/ou reformage
JP7219474B2 (ja) 複合酸化物、金属担持物及びアンモニア合成触媒
US9475037B2 (en) Nickel hexaaluminate-containing catalyst for reforming hydrocarbons in the presence of carbon dioxide
EP2033943B1 (fr) Catalyseur pour la méthanation de monoxyde de carbone, procédé de préparation du catalyseur et procédé de méthanation
WO2015091310A1 (fr) Procédé de reformage de mélanges d'hydrocarbures et de dioxyde de carbone
WO2013118078A1 (fr) Catalyseur contenant de l'hexaaluminate pour le reformage d'hydrocarbures et procédé de reformage
JP7464738B2 (ja) アンモニア分解触媒
US10987660B2 (en) Hexaaluminate-comprising catalyst for the reforming of hydrocarbons and a reforming process
JP2021130100A (ja) アンモニア分解触媒
EP2866930A1 (fr) Procédé haute pression permettant de soumettre des hydrocarbure à un reformage au dioxyde de carbone réalisé en présence de matière actives contenant de l'iridium
KR101437072B1 (ko) 효율적인 이산화탄소 전환 촉매 및 이의 제조 방법
DE2420945A1 (de) Katalysator fuer die umsetzung von dampf mit kohlenwasserstoffen
WO2018219986A1 (fr) Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant de l'iridium et/ou du rhodium
Squire et al. In situ X-ray diffraction study of lanthanum oxide catalysts during the oxidative coupling of methane
CN103796949A (zh) 在绝热反应级联中使用氧化铈催化剂制备氯气的方法
Dongmei et al. Steam reforming of dimethyl ether over coupled catalysts of CuO-ZnO-Al2O3-ZrO2 and solid-acid catalyst
WO2000016900A1 (fr) Catalyseurs et procede de reformage a la vapeur d'hydrocarbures
WO2018219992A1 (fr) Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant du nickel et des spinelles de magnésium
KR102346850B1 (ko) 삼산화황의 전환 및 수소 생산 방법을 위한 촉매 조성물
Soisuwan et al. Characteristics and catalytic properties of alumina–zirconia mixed oxides prepared by a modified Pechini method
JPH0371174B2 (fr)
Bracciale et al. Steam reforming of model compounds from biomass fermentation over nanometric ruthenium modified nickel-lanthanum perovskites catalysts
KR101950928B1 (ko) 알코올 합성용 촉매, 이의 제조방법 및 그의 용도
Perez-Luna et al. Study of alumina-promoted SO 2-4/NiO/ZrO 2 catalyst performance
CN117751014A (zh) 用于重质烃进料的蒸汽重整催化剂

Legal Events

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

Ref document number: 18726177

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18726177

Country of ref document: EP

Kind code of ref document: A1