WO2013135656A1 - Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal (mélange de métaux des terres rares) sous forme d'hexaaluminates - Google Patents

Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal (mélange de métaux des terres rares) sous forme d'hexaaluminates Download PDF

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WO2013135656A1
WO2013135656A1 PCT/EP2013/054942 EP2013054942W WO2013135656A1 WO 2013135656 A1 WO2013135656 A1 WO 2013135656A1 EP 2013054942 W EP2013054942 W EP 2013054942W WO 2013135656 A1 WO2013135656 A1 WO 2013135656A1
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reaction
catalyst
carbon dioxide
mixed metal
metal oxide
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PCT/EP2013/054942
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German (de)
English (en)
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Leslaw Mleczko
Daniel Gordon Duff
Alexander Karpenko
Emanuel Kockrick
Vanessa GEPERT
Albert TULKE
Daniel Wichmann
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Bayer Intellectual Property Gmbh
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
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    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
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    • B01J8/0496—Heating or cooling the reactor
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
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    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00398—Controlling the temperature using electric heating or cooling elements inside the reactor bed
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    • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00522—Controlling the temperature using inert heat absorbing solids outside the bed
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/2402—Monolithic-type reactors
    • B01J2219/2409—Heat exchange aspects
    • B01J2219/2416—Additional heat exchange means, e.g. electric resistance heater, coils
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/2402—Monolithic-type reactors
    • B01J2219/2425—Construction materials
    • B01J2219/2427—Catalysts
    • B01J2219/2428—Catalysts coated on the surface of the monolith channels
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/2402—Monolithic-type reactors
    • B01J2219/2425—Construction materials
    • B01J2219/2427—Catalysts
    • B01J2219/243—Catalyst in granular form in the channels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • 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 present invention relates to a process for reducing carbon dioxide comprising the step of reacting carbon dioxide and hydrogen in the presence of a catalyst to form carbon monoxide and water.
  • the invention further relates to the use of such a catalyst in the reduction of carbon dioxide.
  • WGS water gas shift reaction
  • WO 2008/055776 A1 discloses a process for preparing a catalytic composition comprising a catalytically active metal and a solid support, wherein a portion of the catalytically active metal is distributed on the outer surface of the support and another part in the core structure of the solid support and wherein the solid support is a refractory oxide and ion-conducting oxide.
  • WO 2008/031024 A1 describes a solid-state membrane for a reforming reactor which comprises at least one anion-conducting oxide from the group of hexaaluminates, cerates, perovskites and other mixed metal oxides which can adsorb and dissociate molecular oxygen.
  • the membrane absorbs and dissociates molecular oxygen to highly active atomic oxygen and allows oxygen anions to permeate through the membrane. Thus, a high local concentration of oxygen is achieved to prevent the formation and deposition of carbon deposits on the reformer walls.
  • Embodiments of the membrane also have a catalytic activity in the reforming of hydrocarbons to synthesis gas.
  • a reformer having an interior wall incorporating the novel membrane is disclosed, as well as a process for reforming hydrocarbons, such as high sulfur diesel fuel, to produce synthesis gas for use in fuel cells.
  • WO 2009/058584 A2 relates to a water gas shift catalyst comprising a noble metal deposited on a carrier, wherein the carrier is obtained from a mixture comprising A low surface area material such as an aluminate and especially a hexaaluminate and a high surface area material such as a mixed metal oxide, particularly a mixture of zirconium oxide and cerium oxide, which also includes one or more of the high surface area transition metal aluminate group Alkali or Erdalkalidot istsstoff and an additional dopant from the group Ga, Nd, Pr, W, Ge, Au, Ag, Fe, their oxides and mixtures thereof can be added.
  • a low surface area material such as an aluminate and especially a hexaaluminate
  • a high surface area material such as a mixed metal oxide, particularly a mixture of zirconium oxide and cerium oxide, which also includes one or more of the high surface area transition metal aluminate group Alkali or Erdalkalidot
  • WO 2005/026093 A1 describes a process for the preparation of dimethyl ether (DME), which involves the separation of a CO 2 -rich stream from a crude product stream with DME and CO 2 from a synthesis of DME via synthesis gas.
  • the CO 2 -rich stream is introduced into an RWGS reactor in which it reacts with hydrogen in the presence of a catalyst to give a CO rich stream.
  • the CO-rich stream is returned to the methanol synthesis step.
  • much of the CO 2 gas from the production of DME can be recycled, thereby increasing the yield of DME and reducing the amount of CO2 released.
  • Naoufal et al. Catalysis Letters (1998), 54, 141-148) describes the synthesis, structure and catalytic properties in the methane oxidation of Fe-substituted barium hexaaluminates.
  • the present invention has therefore set itself the task of providing a method for carrying out the RWGS reaction, which can be operated with a low-cost catalyst with high activity and selectivity and a long-term stability at high temperatures.
  • This object is achieved by a method for the reduction of carbon dioxide, comprising the step of the reaction of carbon dioxide and hydrogen in the presence of a catalyst to form carbon monoxide and water, wherein the reaction is carried out at a temperature of> 700 ° C and the catalyst Mixed metal oxide includes which
  • (I) is an oxide of the general formula LO (Al 2 O 3) z ;
  • reaction products of (I) in the presence of a gas mixture comprising carbon dioxide, hydrogen, carbon monoxide and water at a temperature of> 700 ° C comprises;
  • L is selected from the group: 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; and
  • the catalysts used according to the invention or their conversion products under the prevailing reaction conditions are stable catalysts which are comparable with industrial benchmark systems in at least one respect.
  • the RWGS reaction can be selectively operated at the elevated temperatures according to the invention.
  • the present invention relates to the recovery of CO and H 2 O by RWGS reaction. This is in contrast to the WGS reaction, where possibly the back reaction also leads to CO and H2O.
  • the process according to the invention is preferably carried out such that the conversion of CO 2 after completion of the reaction (in particular after leaving a reactor such as, for example, an axial flow reactor) is more than 35 mol%, preferably more than 40 mol%, more preferably more than 45 mol% and most preferably above 50 mole%.
  • LAI12O19 or LAI11O18 can be considered. This may alternatively be expressed as LO (Ab03) 6 or LOi, 5 (Ab03) 5.5.
  • L are in particular Ba, Sr, Ca, La, ... and other metals of alkaline earth (Group 2) and rare earths (lanthanides) and mixtures thereof.
  • Hexaaluminate materials may also be referred to as "aluminates” (see US 2009/01 96822 A1) or “stabilized alumina” or “doped alumina” (also called “beta alumina”).
  • the formula can be postulated such that the ratio between LO and Al2O3, namely the parameter z in the structural formula LO (M ( y / Z ) Al (2 - y / Z ) 03) z, according to 4 ⁇ z ⁇ 9 is varied.
  • L can also stand for a mixture of several divalent and / or trivalent cations (L, L ', L ",).
  • Hexaaluminate materials may also be referred to as “aluminates” (see US 2009/01 96822 A I) or “stabilized alumina” or “doped alumina” (also called “beta alumina”).
  • aluminates see US 2009/01 96822 A I
  • stabilized alumina or “doped alumina”
  • doped alumina also called “beta alumina”
  • the term is used in a broader sense, as stated above (4 ⁇ z ⁇ 9).
  • hexaaluminates In the preparation of the hexaaluminates to be used according to the invention, perfect homogeneity of the generalized hexaaluminate phase should not be assumed. Multiple phases may already be present in practice after precipitation and calcination, although the hexaaluminates predominate in the broad sense.
  • phase-separated portions of the catalytically active dopants L (and L ', L ", ...), if there is more than one, can be alloyed or mixed in one another All in all, mixtures of the different states are possible, both under reaction conditions and
  • directly at the fresh catalytic converter ie, some states of the active components are possible side by side, with metal elements incorporated in the carrier grid and also outside can be present simultaneously, as well as metal elements mixed as mixed metal oxide (or as a metal alloy) and can also be separated / segregated.
  • aluminas doped with "L” or the "L” containing aluminates in particular including the L-hexaaluminates are characterized by a particular thermal stability against sintering. Without being bound by theory, this could be related to the surprising stability of catalytic activity at high temperatures.
  • a physical mixture of oxidic constituents of a hexaaluminate, for example LO and M Ox mixed with gamma-AhC, which at least temporarily turns into a hexaaluminate structure under reaction conditions at high temperatures, is also part of the present invention.
  • catalysts to be used according to the invention in particular barium, strontium and calcium hexaaluminates are suitable.
  • Mixed metal oxides of type (I) can be prepared, inter alia, by physical (such as PVD) and chemical methods, the latter mainly in the solid phase or liquid phase. Examples include precipitation, co-precipitation, sol-gel process, impregnation, ignition / combustion methods and further gas phase methods such as CVD.
  • physical such as PVD
  • chemical methods the latter mainly in the solid phase or liquid phase. Examples include precipitation, co-precipitation, sol-gel process, impregnation, ignition / combustion methods and further gas phase methods such as CVD.
  • reaction products includes the catalyst phases present under reaction conditions.
  • the gas mixture to which the catalyst is exposed during the reaction comprising carbon dioxide, hydrogen, carbon monoxide and water may contain these four components, for example, in a content of> 80% by weight, preferably> 90% by weight and more preferably> 95% by weight> contain.
  • a reaction temperature of> 700 ° C is provided.
  • the reaction temperature is> 850 ° C, and more preferably> 900 ° C.
  • a hydrocarbon having 1 to 4 C atoms is added during the reaction.
  • Suitable hydrocarbons are, in particular, alkanes having 1 to 4 C atoms, methane being particularly suitable.
  • the addition of the hydrocarbon takes place at arbitrary positions along the longitudinal axis of the reactor. For example, hydrocarbon addition may occur at the reactor inlet, at the reactor outlet and / or at a position between inlet and outlet.
  • the hydrocarbon may, for example, in a proportion of> 0.01% by volume to ⁇ 20% by volume, preferably> 0.1% by volume to ⁇ 10% by volume and more preferably> 1% by volume to ⁇ 10% by volume >, based on the total volume of the reaction gases to be added.
  • concentration of the hydrocarbon after the reaction is ⁇ 20% by volume, and preferably ⁇ 10% by volume.
  • the mixed metal oxide (I) comprises BaAli20i9, SrAli20i9 and / or CaAli20i9.
  • the mixed metal oxide (I) BaAli20i9, SrAli 2 0i9 and / or CaAli 2 0i9.
  • the reaction is carried out at a temperature of> 700 ° C to ⁇ 1300 ° C. More preferred ranges are> 800 ° C to ⁇ 1200 ° C and> 900 ° C to ⁇ 1100 ° C, especially> 850 ° C to ⁇ 1050 ° C.
  • the reaction is carried out at a pressure of> 1 bar to ⁇ 200 bar.
  • the pressure is> 2 bar to ⁇ 50 bar, more preferably> 10 bar to ⁇ 30 bar.
  • the catalyst is applied to a support and the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • An example of this is SiC. Further preferred is cordierite.
  • the reaction is operated in autothermal mode.
  • This can be achieved, for example, both by the addition of oxygen in the educt gas, as well as that hydrogen-rich residual gases such as anode residual gas, PSA residual gas, natural gas (preferably methane) and / or additional hydrogen in the presence of CO 2 fuel gas sources.
  • Another object of the present invention is the use of a catalyst comprising a mixed metal oxide in the reaction of carbon dioxide and hydrogen, wherein carbon monoxide and water are formed, wherein the catalyst comprises a mixed metal oxide, which (I) an oxide of the general formula LO (Al203) z is; and or
  • reaction products of (I) in the presence of a gas mixture comprising carbon dioxide, hydrogen, carbon monoxide and water at a temperature of> 700 ° C comprises; where L is selected from the group: 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; and
  • reaction products includes the catalyst phases present under reaction conditions.
  • the mixed metal oxide (I) comprises BaAli20i9, SrAli20i9 and / or CaAli20i9.
  • the mixed metal oxide (I) BaAli20i9, SrAli20i9 and / or CaAli20i9.
  • the catalyst is applied to a support and the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • An example of this is SiC.
  • Further preferred is cordierite.
  • FIG. 1 shows schematically an expanded view of a reactor for carrying out the method according to the invention.
  • FIG. Figure 2 shows turnover curves for CO 2 in various RWGS experiments
  • the reaction can be carried out in a flow reactor, which seen in the flow direction of the reaction gases, a plurality of heating levels 100, 101, 102, 103, which are electrically heated by means of heating elements 1 10, 11 1, 112, 1 13, wherein the heating levels 100, 101, 102, 100 can be flowed through by the reaction gases, wherein at least one heating element 110, 11 1, 1 12, 1 13 the catalyst is arranged and there is heated and at least once an intermediate level 200, 201, 202 between two heating levels 100, 101, 102, 103 is arranged, wherein the intermediate level 200, 201, 202 also from the reaction gases can be flowed through.
  • the reactor has a plurality of (four in the present case) heating levels 100, 101, 102, 103, which are electrically heated by means of corresponding heating elements 110, 111, 112, 113.
  • the heating levels 100, 101, 102, 103 are flowed through during operation of the reactor by the reaction gases and the heating elements 1 10, 111, 112, 113 are contacted by the reaction gases.
  • At least one heating element 110, 111, 112, 113, the catalyst is arranged and is heated there.
  • the catalyst may be directly or indirectly connected to the heating elements 1 10, 1 1 1, 1 12, 1 13, so that these heating elements represent the catalyst support or a support for the catalyst support.
  • the heat supply of the reaction takes place electrically and is not introduced from the outside by means of radiation through the walls of the reactor, but directly into the interior of the reaction space. It is realized a direct electrical heating of the catalyst.
  • heating elements 110, 111, 112, 113 are preferably Bankleiterlegtechniken such as FeCrAl alloys used.
  • metallic materials it is also possible to use electrically conductive Si-based materials, particularly preferably SiC, and / or carbon-based materials.
  • At least one intermediate ceramic level 200, 201, 202 (which is preferably supported by a ceramic or metal support framework / plane) is arranged between two heating levels 100, 101, 102, 103, the intermediate level (n ) 200, 201, 202 or the contents 210, 21 1, 212 of an intermediate level 200, 201, 202 are also flowed through in the operation of the reactor from the reaction gases. This has the effect of homogenizing the fluid flow. It is also possible that additional catalyst is present in one or more intermediate levels 200, 201, 202 or other isolation elements in the reactor. Then an adiabatic reaction can take place.
  • the pressure in the reactor can take place via a pressure-resistant steel jacket.
  • suitable ceramic insulation materials it can be achieved that the pressure-bearing steel is exposed to temperatures of less than 200 ° C and, if necessary, less than 60 ° C.
  • the electrical connections are shown in FIG. 1 only shown very schematically. They can be performed in the cold area of the reactor within an insulation to the ends of the reactor or laterally from the heating elements 110, 1 1 1, 1 12, 1 13 carried out so that the actual electrical connections can be provided in the cold region of the reactor.
  • the electrical heating is done with direct current or alternating current.
  • the use of the electrically heated elements in the inlet region of the reactor also has a positive effect with regard to the cold start and starting behavior, in particular with regard to rapid heating to the reaction temperature and better controllability.
  • the catalyst can in principle be present as a loose bed, as a washcoat or else as a monolithic shaped body on the heating elements 110, 111, 112, 113. However, it is preferred that the catalyst is directly or indirectly connected to the heating elements 110, 11 1, 112, 11, so that these heating elements constitute the catalyst support or a support for the catalyst support.
  • heating levels 100, 101, 102, 103 heating elements 1 10, 1 1 1, 1 12, 1 13 are arranged, which are constructed in a spiral, meandering, lattice-shaped and / or reticulated.
  • the (for example ceramic) intermediate levels 200, 201, 202 or their contents 210, 21 1, 212 comprise a material resistant to the reaction conditions, for example a ceramic foam. They serve for mechanical support of the heating levels 100, 101, 102, 103 and for mixing and distribution of the gas stream. At the same time an electrical insulation between two heating levels is possible. It is preferred that the material of the content 210, 211, 212 of an intermediate level 200, 201, 202 oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium. An example of this is SiC. Further preferred is cordierite.
  • the intermediate level 200, 201, 202 may include, for example, a loose bed of solids. These solids themselves may be porous or solid, so that the fluid flows through gaps between the solids. It is preferred that the material of the solid bodies comprises oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium. An example of this is SiC. Further preferred is cordierite.
  • the intermediate plane 200, 201, 202 comprises a one-piece porous solid.
  • the fluid flows through the intermediate plane via the pores of the solid.
  • honeycomb monoliths as used for example in the exhaust gas purification of internal combustion engines.
  • the average length of a heating level 100, 101, 102, 103 is viewed in the direction of flow of the fluid and the average length of an intermediate level 200, 201, 202 in the direction of flow of the fluid is in a ratio of> 0.01: 1 to ⁇ 100: 1 to each other. Even more advantageous are ratios of> 0.1: 1 to ⁇ 10: 1 or 0.5: 1 to ⁇ 5: 1.
  • At least one heating element 110, 111, 112, 113 can have a different amount and / or type of catalyst from the other heating elements 110, 111, 112, 113.
  • the heating elements 110, 111, 112, 113 are arranged so that they can each be electrically heated independently of each other. Accordingly, in the method according to the invention, the individual heating elements 110, 111, 112, 113 can be operated with a different heating power.
  • the individual heating levels can be individually controlled and regulated.
  • inlet area can be dispensed with a catalyst in the heating levels as needed, so that only the heating and no reaction takes place in the inlet area. This is particularly advantageous in terms of starting the reactor.
  • a temperature profile adapted for the respective reaction can be achieved. With regard to the application for endothermic equilibrium reactions, this is, for example, a temperature profile which achieves the highest temperatures and thus the highest conversion at the reactor outlet.
  • the reactor can be modular.
  • a module may include, for example, a heating level, an intermediate level, the electrical contact and the corresponding further insulation materials and thermal insulation materials.
  • Example 1 Barium hexaaluminate by co-precipitation
  • the catalyst was crushed and calcined for 5 hours at 1300 ° C under air atmosphere.
  • Example 2 Co-precipitated strontium hexaaluminate A portion of Sr (NÜ3) 2 (10 mmol) was dissolved in 100 ml of hot deionized water and adjusted to pHl by adding concentrated nitric acid. A portion of A1 (NO 3) 3.9H 2 O (120 mmol) was added with stirring and allowed to dissolve completely.
  • the catalyst was crushed and calcined for 5 hours at 1300 ° C under air atmosphere.
  • FIG. 2 illustrates the CO2 turnover curves over the reaction time for these catalysts.
  • the thermodynamic limitation at about 60% conversion is indicated by "TD”. It can be seen that for Ba-based systems higher activities result than for comparable Sr structures.

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Abstract

La présente invention concerne un procédé de réduction de dioxyde de carbone qui consiste à mettre en réaction du dioxyde de carbone et de l'hydrogène en présence d'un catalyseur, avec formation de monoxyde de carbone et d'eau, caractérisé en ce que la réaction est réalisée à une température > 700°C et en ce que le catalyseur comprend un oxyde de mischmétal (mélange de métaux des terres rares) qui est (I) un oxyde de formule générale LO(Al2O3)z et/ou (II) des produits de réaction de (I) en présence d'un mélange gazeux comprenant du dioxyde de carbone, de l'hydrogène, du monoxyde de carbone et de l'eau, à une température > 700°C. Selon l'invention : L est choisi dans le groupe formé par : 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 et/ou Lu; et 4 < z < 9. Dans certains exemples, l'oxyde de mischmétal comprend BaAl12O19 ou SrAl12O19 ou CaAl12O19.
PCT/EP2013/054942 2012-03-13 2013-03-12 Procédé de réduction de dioxyde de carbone à hautes températures sur des catalyseurs à oxyde de mischmétal (mélange de métaux des terres rares) sous forme d'hexaaluminates WO2013135656A1 (fr)

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CN107930637A (zh) * 2017-12-05 2018-04-20 内蒙古科技大学 一种稀土基含铁高熵固溶体催化剂及其制备方法

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