EP3826789A1 - Élément en mousse métallique contenant du cobalt et son procédé de production - Google Patents

Élément en mousse métallique contenant du cobalt et son procédé de production

Info

Publication number
EP3826789A1
EP3826789A1 EP20775651.1A EP20775651A EP3826789A1 EP 3826789 A1 EP3826789 A1 EP 3826789A1 EP 20775651 A EP20775651 A EP 20775651A EP 3826789 A1 EP3826789 A1 EP 3826789A1
Authority
EP
European Patent Office
Prior art keywords
metal foam
foam body
aluminum
metal
catalytically active
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
EP20775651.1A
Other languages
German (de)
English (en)
Inventor
René Poss
Meike Roos
Monika BERWEILLER
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.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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 Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP3826789A1 publication Critical patent/EP3826789A1/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B01J37/0226—Oxidation of the substrate, e.g. anodisation
    • 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
    • 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
    • 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
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1146—After-treatment maintaining the porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C22C1/083—Foaming process in molten metal other than by powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B22F2003/242—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B22F2003/244—Leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • B22F2007/042—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method
    • B22F2007/045—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method accompanied by fusion or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • B22F2007/042—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method
    • B22F2007/047—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method non-pressurised baking of the paste or slurry containing metal powder
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    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/05—Light metals
    • B22F2301/052—Aluminium
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    • B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms

Definitions

  • the present invention relates to processes for the production of supported catalysts, which comprise the following steps: coating of metal foam bodies made of metallic cobalt, an alloy of nickel and cobalt, or an arrangement of superimposed layers of nickel and cobalt with aluminum, subsequent thermal treatment in order to form an alloy achieve between metal foam and aluminum, subsequent oxidative treatment of the aluminum surface, as well as application of a catalytically active layer, which comprises at least one carrier oxide and at least one catalytically active component.
  • the present invention also relates to the supported catalysts obtainable by the process and their use in chemical transformations.
  • the use of metal foams as support bodies for catalytically active coatings is known from the prior art.
  • the catalytically active coatings on the metallic support bodies are typically composed of a carrier oxide which enlarges the microscopic surface and catalytically active metals which are applied to the carrier oxide (cf. e.g. WO 9511752 A1).
  • the monolithic supported catalysts obtained in this way can be used in a wide variety of applications, but their usability is limited by the extremely poor adhesion of the catalytically active coating, which is mainly composed of oxidic components, to the metallic support body.
  • sol-gel processes are used as catalyst support bodies for coating metal foams.
  • these processes require special equipment and the use of expensive reagents, which have a high hazard potential and are difficult to handle.
  • ALD atomic layer deposition
  • US 20120329889 A1 discloses a method for producing metal foam support catalysts for the Fischer-Tropsch synthesis, in which a thin ALOs film is produced on a metal foam by “atomic layer deposition” (ALD) and then an oxidic coating by dip coating, drying and subsequent calcination is applied.
  • US 20120329889 A1 explicitly points out that a stable coupling between the metal foam surface and the oxidic coating is difficult to achieve (cf. paragraphs [0068] - [0069]), and that this is achieved by applying the oxidic intermediate layer by means of ALD.
  • the present invention is a.
  • Processes according to the invention for the production of supported catalysts comprise the following steps:
  • a catalytically active layer comprising at least one carrier oxide and at least one catalytically active component, to at least part of the surface of metal foam body C, so that a supported catalyst is obtained.
  • nickel foam bodies onto which aluminum is first applied, alloyed and then partially leached again, are known as an alternative to classic Raney-type catalysts (cf., for example, EP 2764916 A1).
  • the foam bodies thus obtained are activated all-metal catalysts of the Raney type, which are typically used in hydrogenation reactions.
  • Metal foam bodies are also known from the prior art, onto which aluminum is first applied and alloyed and which are then oxidized (cf. Wen-Wen Zeng et al. “Synthesis and compression property of oxidation-resistant Ni-Al foams”, Acta metallurgica Sinica, Volume 30, No. 10, October 1, 2017, pages 965-972).
  • Wen-Wen Zeng et al. “Synthesis and compression property of oxidation-resistant Ni-Al foams”, Acta metallurgica Sinica, Volume 30, No. 10, October 1, 2017, pages 965-972).
  • the alloy formation is limited to the upper layers of the metal foam, so that unalloyed areas remain in central regions of the metal foam.
  • metal foam body A is understood to mean a foam-shaped metal body.
  • Foam-shaped metal bodies are disclosed, for example, in Ullmann's Encyclopedia of Industrial Chemistry, chapter “Metallic Foams”, published online on July 15, 2012, DOI: 10.1002 / 14356007. c16_c01 pub2.
  • metal foams with various morphological properties with regard to pore size and shape, layer thickness, surface density, geometric surface, porosity, etc. are suitable.
  • Metal foam A preferably has a density in the range from 400 to 1500 g / m 2 , a pore size from 400 to 3000 ⁇ m, preferably from 400 to 800 ⁇ m and a thickness in the range from 0.5 to 10 mm, preferably from 1.0 to 5.0 mm.
  • the production can take place in a manner known per se.
  • a foam can be made from an organic polymer are first coated with a metal and then the polymer is removed by thermolysis to obtain a metal foam.
  • the foam composed of the organic polymer can be brought into contact with a solution or suspension which contains the first metal. This can e.g. B. be done by spraying or dipping.
  • a polymer foam suitable for producing moldings in the form of a foam preferably has a pore size in the range from 100 to 5000 ⁇ m, particularly preferably from 450 to 4000 ⁇ m and in particular from 450 to 3000 ⁇ m.
  • a suitable polymer foam preferably has a layer thickness of 0.5 to 10 mm, particularly preferably from 1.0 to 5.0 mm.
  • a suitable polymer foam preferably has a density of 300 to 1200 kg / m 3 .
  • the specific surface area is preferably in a range from 100 to 20,000 m 2 / m 3 , particularly preferably from 1000 to 6000 m 2 / m 3 .
  • the porosity is preferably in a range from 0.50 to 0.95.
  • the metal foam bodies A used in step (a) of the method according to the invention can have any shape, for example cubic, cuboid, cylindrical, etc.
  • the metal foam bodies can, however, also be shaped, for example, into monoliths.
  • step (b) of the process according to the invention can be carried out in a variety of ways, e.g. B. by bringing metal foam body A into contact with a composition of the aluminum-containing powder MP by rolling or dipping, or by applying a composition of the aluminum-containing powder MP by spraying, sprinkling or pouring.
  • the composition of the aluminum-containing powder MP can be present as a suspension or in the form of a powder.
  • step (b) of the method according to the invention is preferably preceded by a prior impregnation of metal foam body A with a binder.
  • the impregnation can take place, for example, by spraying the binder or dipping metal foam body A into the binder, but is not limited to these possibilities.
  • the composition of the metal-containing powder MP can then be applied to the metal foam body A prepared in this way.
  • the binder and composition of the aluminum-containing powder MP can be applied in one step.
  • the composition of the aluminum-containing powder MP is either suspended in the liquid binder itself before application, or the composition of the aluminum-containing powder MP and the binder are suspended in an auxiliary liquid F.
  • the binder is a composition that can be completely converted into gaseous products by thermal treatment in the temperature range from 100 to 400 ° C, comprising an organic compound that promotes adhesion of the composition of the aluminum-containing powder MP to the metal foam body.
  • the organic compound is preferably selected from the following group: polyethyleneimine (PEI),
  • the molecular weight of the polyethyleneimine is preferably in a range from 10,000 to 1,300,000 g / mol.
  • the molecular weight of the polyethyleneimine (PEI) is preferably in a range from 700,000 to 800,000 g / mol.
  • Auxiliary liquid F must be suitable to suspend the composition of the aluminum-containing powder MP and the binder and to be able to be converted completely into gaseous products by thermal treatment in the temperature range from 100 to 400 ° C.
  • Auxiliary liquid F is preferably selected from the following group: water, ethylene glycol, PVP and mixtures of these compounds. If auxiliary liquid is used, the binder is typically suspended in water at a concentration in the range from 1 to 10% by weight, and the composition of the aluminum-containing powder MP is then suspended in this suspension.
  • the aluminum-containing powder MP used in step (b) of the process according to the invention comprises pulverulent aluminum, but can also contain additives which contribute to increasing the flowability or water resistance. Such additives must be able to be converted completely into gaseous products by thermal treatment in the temperature range from 100 to 400 ° C.
  • the aluminum-containing powder MP preferably has an aluminum content in the range from 80 to 99.8% by weight. Powders in which the aluminum particles have a particle size of not less than 5 ⁇ m and not greater than 200 ⁇ m are preferred. Powders in which 95% of the aluminum particles have a particle size of not less than 5 ⁇ m and not greater than 75 ⁇ m are particularly preferred. It is possible that the aluminum-containing powder MP also contains aluminum components in oxidized form in addition to the aluminum component in elemental form. This oxidized fraction is usually in the form of oxidic compounds such as oxides, hydroxides and / or carbonates. The mass fraction of oxidized aluminum is typically in the range from 0.05 to 10% by weight of the total mass of the aluminum-containing powder MP.
  • step (c) of the method according to the invention a thermal treatment takes place in order to achieve the formation of one or more alloys.
  • step (c) of the method according to the invention metal foam body AX is thermally treated in order to achieve alloy formation between metal foam body A and aluminum-containing powder MP, so that metal foam body B is obtained, the highest temperature of the thermal treatment of metal foam body AX in the range from 680 to 715 ° C., and the total duration of the thermal treatment in the temperature range from 680 to 715 ° C. being between 5 and 240 seconds.
  • the thermal treatment usually comprises the step-by-step heating of the metal foam body AX and the subsequent cooling to room temperature.
  • the thermal treatment takes place under inert gas or under reductive conditions.
  • Reductive conditions are understood to mean the presence of a gas mixture which contains hydrogen and at least one gas which is inert under the reaction conditions. Suitable is z. B. a gas mixture that contains 50 vol% N2 and 50 vol% H2.
  • the inert gas used is preferably nitrogen.
  • the heating can, for. B. be done in a belt furnace. Suitable heating rates are in the range from 10 to 200 K / min, preferably 20 to 180 K / min.
  • the temperature is typically first increased from room temperature to about 300 to 400 ° C.
  • the temperature is then increased to in the range from 680 to 715 ° C. and an alloy is formed between the metal foam body A and the aluminum-containing powder MP.
  • the metal foam body is then quenched by contact with the protective gas environment at a temperature of approx. 200 ° C.
  • the highest temperature of the thermal treatment of metal foam body AX in step (c) is in the range from 680 to 715 ° C, and that the total duration of the thermal treatment in the temperature range from 680 to 715 ° C is between 5 and 240 seconds.
  • the duration of the thermal treatment can compensate for the level of the highest treatment temperature and vice versa;
  • the frequency of experiments in which alloying is achieved in the upper area of the metal foam while unalloyed areas remain inside the metal foam decreases sharply if the temperature interval between 680 and 715 ° C at the maximum temperature of the thermal treatment is left and / or the duration of the thermal treatment in the temperature interval between 680 and 715 ° C is outside the range of 5 to 240 seconds. If the maximum temperature is too high and / or if the metal foam body remains in the region of the maximum temperature for too long, the alloy formation progresses into the deepest layers of the metal foam and no unalloyed areas remain. Too low a maximum temperature and / or too short If the metal foam body remains in the range of the maximum temperature, the alloy formation does not even begin.
  • the thermal treatment of the metal foam in step (c) of the process according to the invention leads to the formation of aluminum-containing phases.
  • the ratio V of the masses of metal foam body B to metal foam body A, V m (metal foam body B) / m (metal foam body A), is a measure of how much aluminum was alloyed into the foam in step (c) of the process according to the invention.
  • step (d) of the method according to the invention an oxidative treatment of metal foam body B takes place, so that metal foam body C is obtained.
  • the aim of the oxidative treatment of metal foam body B in step (d) of the method according to the invention is to provide the aluminum present on the surface of metal foam body B with an external aluminum oxide layer.
  • This goal can be achieved, for example, by exposing the metal foam body B either in a heated state to an oxidative gas atmosphere (e.g. air), or by first forming aluminum hydroxide on the surface of the metal foam body B, e.g. by bringing it into contact with an alkaline solution, and then applying the aluminum hydroxide thermal treatment under oxidizing conditions is converted into aluminum oxide.
  • an oxidative gas atmosphere e.g. air
  • the temperature should be selected between 200 ° C and 1200 ° C, or between 200 ° C and 1000 ° C, or between 200 ° C and 750 ° C.
  • the thermal oxidation is preferably carried out over a period of 1 to 60 minutes at a temperature of 200 ° C. to 700 ° C. in air.
  • metal foam body B If aluminum hydroxide is initially formed on the surface of metal foam body B, e.g. by bringing it into contact with an alkaline solution and only then thermally treated, at least some of the aluminum on the surface is first converted to aluminum hydroxide and then at least some of the aluminum hydroxide formed on the surface is converted to aluminum oxide.
  • the conversion of at least part of the aluminum lying on the surface to aluminum hydroxide is preferably achieved by bringing the metal foam body into contact with an aqueous alkaline solution.
  • the aqueous alkaline solution particularly preferably contains sodium hydroxide, potassium hydroxide, lithium hydroxide or a combination thereof in a concentration of 0.05 to 30% by weight, preferably 0.5 to 5% by weight, and metal foam body B is with the aqueous alkaline solution over a period of Brought into contact for 5 to 120 minutes, preferably a maximum of 30 minutes and particularly preferably a maximum of 10 minutes.
  • This treatment can take place in a temperature range between 10 ° C and 110 ° C. Treatment at 20 ° C. (room temperature) is preferred.
  • the aluminum hydroxide formed on the surface is thermally converted to aluminum oxide in an oxidizing atmosphere.
  • the mixture is heated to a temperature of 20 ° C (room temperature) to 700 ° C over a period of 1 minute to 8 hours with the admission of air.
  • the thermal oxidation is preferably carried out over a period of 1 to 60 minutes at a temperature of 200 ° C. to 700 ° C. in air.
  • Metal foam body C serves as a support body for a suitable catalyst, which can be specifically selected for the particular reaction that is to be catalyzed.
  • a catalytically active layer comprising at least one carrier oxide and at least one catalytically active component, is applied to at least part of the surface of metal body C, so that a supported catalyst is obtained.
  • Metal foam bodies C according to the invention can be equipped particularly well with a catalytically active layer according to the invention, since the aluminum oxide skin produced on the surface of metal foam body C ensures extremely good binding of the carrier oxides and a long durability and service life as well as extremely high mechanical stability, in particular abrasion resistance , causes.
  • the catalytically active layer comprising at least one carrier oxide and at least one catalytically active component, can be applied, for example, to metal foam body C by sucking or pumping a coating suspension through the continuous cavities of open-pore metal foam body C.
  • metal foam body C is similar to the monolithic substrates used in car exhaust catalysis.
  • the application of a coating suspension in dipping processes is similar to the monolithic substrates used in car exhaust catalysis.
  • spray coating in spraying processes
  • which of the application methods known in principle in the prior art is to be preferred depends on the one hand on the composition and the flow properties of the coating suspension and on the other hand on the actual structure of the metal foam body according to the invention. Dip coating has the highest possible tolerance to varying properties of the coating suspension and is therefore suitable for coating all metal foam bodies according to the invention.
  • step (e) following the bringing into contact with the coating suspension, the coated metal foam body is calcined and the supported catalyst is thus obtained.
  • the catalytically active layer comprises at least one carrier oxide.
  • carrier oxides are inorganic oxides with high specific surface areas, which are typically between 50 and 200 m 2 / g. These carrier oxides have several functions in the finished catalyst: On the one hand, they serve to enlarge the macroscopic, ie geometric surface provided by the metal foam bodies according to the invention, which in the context of this invention is referred to as the contact surface of the catalyst with the reaction medium, in the microscopic level. On the other hand, they can interact with the catalytically active species and thus influence the course of the reaction.
  • the choice of carrier oxide influences the selectivity of complex hydrogenation reactions in which several functional groups of organic substrate molecules can react with hydrogen. Furthermore, they provide the microscopic surface on which the catalytically active components are distributed. They also form a matrix in which further functional components and additives can be distributed, which are used to set special functions of the catalytic converter when it is adapted to a specific application.
  • Carrier oxides are preferably selected from the group consisting of aluminum oxide, silicon dioxide, titanium oxide and mixtures thereof.
  • Transition metals or compounds of transition metals are used as catalytically active components of the catalytically active layer, the transition metals preferably being selected from the group consisting of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, cerium, copper, Silver, gold and mixtures thereof.
  • the catalytically active layer can contain inorganic oxides, preferably selected from the oxides of the alkaline earth metals, the oxides of the transition metals, the rare earths, the oxides of aluminum and gallium, the oxides of silicon, germanium and tin and / or mixtures thereof.
  • the catalytically active layers according to the present invention can contain one or more carrier oxides, one or more catalytically active components and, if appropriate, further functional components and additives.
  • a coating suspension is produced by introducing the constituents into water.
  • the application of the catalytic components to the carrier oxides takes place either by prior impregnation of the carrier oxides with appropriate metal salt solutions (precursor solutions) or by adding precursor solutions directly to the coating suspension and optionally precipitation or chemically induced deposition or decomposition of the precursor compound on the / the already suspended carrier oxide / s.
  • Functional components and additives can also be introduced in this way or added directly as oxidic solids.
  • all of the constituents of the catalyst resulting from soluble precursors can be added by post-impregnation processes after the carrier oxides have been applied to the metal foam bodies according to the invention.
  • the choice of the preparation method is determined by the target composition and the properties of the resulting catalyst to be set.
  • the catalytically active layer applied to the metal foam bodies in step (e) of the process according to the invention is preferably fixed by calcination in air.
  • this calcination is carried out over a period of 1 minute to 8 hours at a temperature of 200 ° C. to 800 ° C. in air.
  • the calcination is preferably carried out over a period of 1 to 480 minutes at a temperature of 200 ° C. to 680 ° C. in air.
  • the calcination is particularly preferably carried out over a period of 1 to 480 minutes at a temperature of 300 ° C. to 650 ° C. in air.
  • step (d) over a period of 1 to 60 minutes at a temperature of 200 ° C. to 680 ° C. in air and the calcination in step (e) over a period of 1 to 480 minutes at a Temperature from 200 ° C to 680 ° C carried out in air.
  • a metal foam body according to the invention forms a pure aluminum oxide layer on the surface due to its excess of Al, which means a diffusion barrier between the carrier material and the catalytic layer.
  • Catalytic layers based on the carrier oxide aluminum oxide and the aluminum oxide on the surface of the metal foam body are systems of the same type.
  • the expansion coefficients are therefore similar, spalling under thermal loads is low and the connection resistance due to a calcination process is very good.
  • the supported catalysts themselves obtainable by these processes and their use in chemical transformations are also a subject of the present invention.
  • Supported catalysts according to the invention can, for example, advantageously be used in chemical fixed bed processes.
  • Binder solution was then sprayed onto metal foam bodies a, b, c, d, e, f (polyethyleneimine (2.5% by weight) in water) and then powdered aluminum (manufacturer: AMG, average particle size: ⁇ 63 ⁇ m, with 3% by weight) % Addition of ethylene bis (stearamide)) applied as a dry powder (approx. 400 g / m 2 ).
  • metal foam bodies a, b, c, d, e were subjected to a thermal treatment in an oven under a nitrogen atmosphere. It was initially heated from room temperature to the maximum temperature in about 15 minutes, this was maintained for a defined period of time and then quenched by contacting with a nitrogen atmosphere of 200 ° C.
  • the extent of the alloy formation in the metal foam bodies was then determined. For this purpose, cross sections of the metal foam bodies were examined under a microscope and a scanning electron microscope. While with the metal foam bodies a, d, e superficial alloy formation has taken place, but unalloyed areas inside the Metal foam have remained, no alloy formation has taken place in metal foam body b, and in metal foam body c the alloy formation has progressed so far that no unalloyed areas remain in the interior of the metal foam.
  • Metal foam body a was exposed to an oxidative gas atmosphere in a heated state.
  • the metal foam body was heated to 700 ° C. in an oven with admission of air.
  • Metal foam body d was first brought into contact with an alkaline solution (5% by weight aqueous NaOH for 10 min at 20 ° C.). A white precipitate forms on the foam. The precipitate is the conversion of aluminum to aluminum hydroxide. Metal foam body d was then dried in air. The dried metal foam body with the white precipitate is pre-oxidized in a preheated oven at 700 ° C. and normal atmosphere, in which the aluminum hydroxide is converted into aluminum oxide.
  • the oxidic pretreatment has several functions:
  • Metal foam body f which had previously remained untreated, was provided with an aluminum oxide layer, as described in the prior art (cf. WO95 / 11752A1, Example 3).
  • metal foam bodies f were completely immersed in a saturated sodium aluminate solution for 3 hours, then swiveled in deionized water until the hydrolysis reaction had subsided, and finally heated at 500 ° C. for 3 hours with access to air.
  • a catalytically active layer was then applied to metal foam bodies a, d, e and f by spraying.
  • the metal foam body was moistened with water.
  • a 2.5% polyethyleneimine suspension was then mixed with c-aluminum oxide with a high surface area.
  • the mixture of water / polyethyleneimine and aluminum oxide was sprayed on.
  • the spraying was followed by a drying process at 140 ° C. for 30 minutes in air in a drying oven.
  • For calcination the sample was baked in an oven at 650 ° C. for 5 hours. The process of coating, drying and calcination was repeated several times until the desired amount of coating was applied. 8. Investigation of the supported catalyst obtained
  • the supported catalysts obtained were examined, among other things the resistance of the catalytically active layer on the metal foam bodies to mechanical stress was examined.
  • a scratch test can be carried out in order to determine the bonding quality of the oxidic, catalytically active layer to the carrier foam. In the present case, however, this test is not possible due to the irregular structure of the foam. Therefore, to investigate the mechanical stability of the catalytically active layer, a temperature change test was carried out, which provides a measure of the quality of the bond between the oxidic layer and the carrier foam.
  • metal foam bodies a, d, e and f were heated to 500 ° C. and then quenched in cold water. The amount lost, i.e. the mass of the flaked catalytic layer of each sample, was then determined by filtering off, drying and weighing the flaked material.
  • Metal foam body a and d 3 mg loss
  • metal foam body f 10 mg loss
  • metal foam body e 50 mg loss
  • Binder solution was then sprayed onto metal foam bodies a, b, c, d, e, f (polyethyleneimine (2.5% by weight) in water) and then powdered aluminum (manufacturer: AMG, average particle size: ⁇ 63 ⁇ m, with 3% by weight) % Addition of ethylene bis (stearamide)) applied as a dry powder (approx. 400 g / m 2 ).
  • metal foam bodies a, b, c, d, e were subjected to a thermal treatment in an oven under a nitrogen atmosphere. It was initially heated from room temperature to the maximum temperature in about 15 minutes, this was maintained for a defined period of time and then quenched by contacting with a nitrogen atmosphere of 200 ° C.
  • the extent of the alloy formation in the metal foam bodies was then determined. For this purpose, cross sections of the metal foam bodies were examined under a microscope and a scanning electron microscope. While with the metal foam bodies a, d, e superficial alloy formation has taken place, but unalloyed areas have remained inside the metal foam, with metal foam body b no alloy formation has taken place, and with metal foam body c the alloy formation has progressed so far that no unalloyed areas inside the Metal foam are left.
  • Metal foam body a was exposed to an oxidative gas atmosphere in a heated state.
  • the metal foam body was heated to 700 ° C. in an oven with admission of air.
  • Metal foam body d was first brought into contact with an alkaline solution (5% by weight aqueous NaOH for 10 min at 20 ° C.). A white precipitate forms on the foam. The precipitate is the conversion of aluminum to aluminum hydroxide. Metal foam body d was then dried in air. The dried metal foam body with the white precipitate is pre-oxidized in a preheated oven at 700 ° C. and normal atmosphere, in which the aluminum hydroxide is converted into aluminum oxide.
  • the oxidic pretreatment has several functions:
  • Metal foam body f which had previously remained untreated, was provided with an aluminum oxide layer, as described in the prior art (cf. WO95 / 11752A1, Example 3).
  • metal foam bodies f were completely immersed in a saturated sodium aluminate solution for 3 hours, then swiveled in deionized water until the hydrolysis reaction had subsided, and finally heated at 500 ° C. for 3 hours with access to air.
  • a catalytically active layer was then applied to metal foam bodies a, d, e and f by spraying.
  • the metal foam body was moistened with water.
  • a 2.5% polyethyleneimine suspension was then mixed with c-aluminum oxide with a high surface area.
  • the mixture of water / polyethyleneimine and aluminum oxide was sprayed on.
  • the spraying was followed by a drying process at 140 ° C. for 30 minutes in air in a drying oven.
  • For calcination the sample was baked in an oven at 650 ° C. for 5 hours. The process of coating, drying and calcination was repeated several times until the desired amount of coating was applied.
  • the supported catalysts obtained were examined, among other things the resistance of the catalytically active layer on the metal foam bodies to mechanical stress was examined.
  • a scratch test can be carried out in order to determine the bonding quality of the oxidic, catalytically active layer to the carrier foam. In the present case, however, this test is not possible due to the irregular structure of the foam. Therefore, to investigate the mechanical stability of the catalytically active layer, a temperature change test was carried out, which provides a measure of the quality of the bond between the oxidic layer and the carrier foam.
  • metal foam bodies a, d, e and f were heated to 500 ° C. and then quenched in cold water. The amount lost, i.e. the mass of the flaked catalytic layer of each sample, was then determined by filtering off, drying and weighing the flaked material.
  • Metal foam body a and d 4 mg loss
  • metal foam body f 12 mg loss
  • metal foam body e 48 mg loss

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Abstract

La présente invention concerne un procédé de production de catalyseurs supportés, consistant à : fournir un élément de mousse métallique A, qui est constitué de cobalt métallique, d'un alliage de nickel et de cobalt, ou d'un agencement de couches de nickel et de cobalt reposant l'une sur l'autre ; appliquer une poudre contenant de l'aluminium MP sur l'élément de mousse métallique A afin d'obtenir un élément de mousse métallique AX ; traiter thermiquement l'élément de mousse métallique AX pour obtenir la formation d'un alliage entre l'élément de mousse métallique A et la poudre contenant de l'aluminium MP, afin d'obtenir un élément de mousse métallique B ; traiter par oxydation l'élément de mousse métallique B afin d'obtenir un élément de mousse métallique C ; et appliquer une couche catalytiquement active, comprenant au moins un oxyde support et au moins un composant catalytiquement actif, sur au moins une partie de la surface de l'élément de mousse métallique C afin d'obtenir un catalyseur supporté. La présente invention concerne en outre les catalyseurs supportés qui peuvent être obtenus à l'aide du procédé et l'utilisation desdits catalyseurs supportés dans des transformations chimiques.
EP20775651.1A 2019-09-25 2020-09-25 Élément en mousse métallique contenant du cobalt et son procédé de production Pending EP3826789A1 (fr)

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Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
EP3300799A1 (fr) 2016-09-30 2018-04-04 Evonik Degussa GmbH Procédé et catalyseur de production de 1,4-butanediol
EP3300798A1 (fr) 2016-09-30 2018-04-04 Evonik Degussa GmbH Lit fixe de catalyseur comprenant de la mousse métallique
WO2019158456A1 (fr) 2018-02-14 2019-08-22 Evonik Degussa Gmbh Procédé de préparation d'alcools en c3-c12 par hydrogénation catalytique des aldéhydes correspondants
EP3797901B1 (fr) 2019-09-25 2021-09-08 Evonik Operations GmbH Corps alvéolaire métallique et son procédé de fabrication
ES2920969T3 (es) 2019-09-25 2022-08-12 Evonik Operations Gmbh Reactor catalítico
CN115305427B (zh) * 2022-09-05 2024-04-05 常德力元新材料有限责任公司 一种铝镍泡沫合金生产装置

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5588194A (en) 1993-10-27 1995-05-22 Scientific Dimensions Usa, Inc. Open cell foam structures, catalysts supported thereby and method of producing the same
JP2003507161A (ja) * 1999-08-17 2003-02-25 バッテル・メモリアル・インスティチュート フィッシャー・トロプシュ合成の触媒構造及び方法
GB0312968D0 (en) * 2003-06-05 2003-07-09 Bp Chem Int Ltd Process for the production of olefins
JP2005205265A (ja) * 2004-01-20 2005-08-04 Materials & Energy Research Institute Tokyo Ltd 触媒体、その製造方法及び水素発生方法
CN101391222A (zh) * 2007-09-21 2009-03-25 汉能科技有限公司 一种泡沫金属改性用混合浆料及其应用
CN101537360B (zh) * 2008-03-17 2012-07-04 汉能科技有限公司 一种固定床雷尼镍催化剂的制备方法
CN101537361B (zh) * 2008-03-21 2012-09-05 汉能科技有限公司 一种固定床雷尼镍催化剂的制备方法
CN101254466A (zh) * 2008-03-25 2008-09-03 浙江大学 负载型雷尼催化剂的制备方法
CN101549297B (zh) * 2008-03-31 2012-09-05 汉能科技有限公司 一种固定床雷镍催化剂的制备方法
KR101094077B1 (ko) * 2010-02-16 2011-12-15 한국에너지기술연구원 금속 폼 표면에 코발트 촉매 분말이 코팅된 코발트 금속 폼 촉매의 제조방법 및 그 코발트 금속 폼 촉매, 이 코발트 금속 폼 촉매를 이용한 열매체 순환 열교환형 반응기 및 이 열매체 순환 열교환형 반응기를 이용한 피셔-트롭쉬 합성 반응에 의한 액체 연료의 생산 방법
KR101212786B1 (ko) * 2010-08-10 2012-12-14 프라운호퍼-게젤샤프트 츄어 푀르더룽 데어 안게반텐 포르슝에.파우. 개방-다공성 금속폼 및 그의 제조방법
EP2764916B1 (fr) 2013-02-06 2017-06-28 Alantum Europe GmbH Corps en mousse métallique à surface modifiée, son procédé de production et son utilisation
FR3009973B1 (fr) * 2013-08-30 2023-06-09 Air Liquide Materiau de pre-revetement d’un substrat metallique d’un materiau catalytique a base de ceramique
EP3300798A1 (fr) * 2016-09-30 2018-04-04 Evonik Degussa GmbH Lit fixe de catalyseur comprenant de la mousse métallique
DE102017202404A1 (de) * 2017-02-15 2018-08-16 Evonik Degussa Gmbh Verfahren zur Herstellung von Isophoronaminoalkohol (IPAA)

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EP3826788A1 (fr) 2021-06-02
KR20220069941A (ko) 2022-05-27
US20220362757A1 (en) 2022-11-17
CN114531855A (zh) 2022-05-24
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WO2021058705A1 (fr) 2021-04-01
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