WO2017137305A1 - Procédé de production d'un corps moulé à action catalytique et corps moulé à action catalytique - Google Patents

Procédé de production d'un corps moulé à action catalytique et corps moulé à action catalytique Download PDF

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Publication number
WO2017137305A1
WO2017137305A1 PCT/EP2017/052270 EP2017052270W WO2017137305A1 WO 2017137305 A1 WO2017137305 A1 WO 2017137305A1 EP 2017052270 W EP2017052270 W EP 2017052270W WO 2017137305 A1 WO2017137305 A1 WO 2017137305A1
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WO
WIPO (PCT)
Prior art keywords
catalytically active
shaped body
tube
alloy
cellular structure
Prior art date
Application number
PCT/EP2017/052270
Other languages
German (de)
English (en)
Inventor
Florian Enzenberger
Ralf GUSCHELBAUER
Carolin KÖRNER
Matthias LODES
Peter Wasserscheid
Original Assignee
Friedrich-Alexander-Universität Erlangen-Nürnberg
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 Friedrich-Alexander-Universität Erlangen-Nürnberg filed Critical Friedrich-Alexander-Universität Erlangen-Nürnberg
Publication of WO2017137305A1 publication Critical patent/WO2017137305A1/fr

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Classifications

    • 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
    • B01J25/00—Catalysts of the Raney type
    • 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
    • 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
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers

Definitions

  • the invention relates to a process for the preparation of a catalytically active molding and a catalytically active molding.
  • Raney catalysts are well known. It is a z. B. formed from porous copper particles powder.
  • porous copper particles is based on powder particles, which are formed for example from a CuAI 2 alloy.
  • the Al contained in the alloy is selectively removed by means of an alkali.
  • Wainwright, MS (1996): Preparation and Utilization of Raney Copper and Raney Copper-Zinc catalysts, Chem. Ind. (Catalyses of Organic Reactions) 68, pp. 213-230.
  • the starting powder used to prepare a Raney catalyst may e.g. B. by quenching a heated to a temperature of about 1 .400 ° C precursor alloy can be produced.
  • Raney catalysts or coated with Raney powder moldings require a lot of effort. Powdered or granulated Raney catalysts are subject to mechanical wear. Moldings which are coated with a Raney powder must first be laboriously prepared and subsequently coated.
  • the object of the invention is to provide a simple and inexpensive feasible method for producing a catalytically active molding.
  • a catalytically active molded body is to be specified, which can be produced easily and inexpensively in a predetermined geometry.
  • an "additive shaping process” is understood as meaning a process in which a shaped body is produced in layers by adding material.
  • the added material is heat sealed or sintered along predetermined portions along predetermined portions with an underlying material.
  • the material is usually in powder form and can be layered, for example, by means of a laser or a laser
  • Additive shaping processes are also particularly suitable for the production of metallic moldings. They are also referred to as 3D printing processes.
  • a "shaped body” is understood to mean a body which has been produced in accordance with a predetermined geometry by means of an additive shaping method.
  • the shaped body according to the present invention has a macroscopic support structure and a microscopic porosity.
  • the macroscopic support structure may be a cellular structure, which in particular comprises a planar structure with openings, a framework structure, tubular or tubular structures or the like.
  • An “alloy” in the sense of the present invention comprises a first and a second element.
  • the second element can be selectively removed from the alloy by means of the liquid phase.
  • a surface having a porous structure substantially composed of the first element results.
  • the remaining as a result of the selective removal of the second element first element is catalytically active or catalytically activated.
  • the "liquid phase” is chosen so that essentially the second element is removed from the alloy.
  • the first element is fundamentally not soluble in the liquid phase or can not be attacked by the liquid phase. However, it may well be that particles formed from the first element are also removed from the alloy when held by bridges formed from the second element and these bridges are removed by the action of the liquid phase. In this case, although particles formed from the first element are removed from the shaped body. Nevertheless, they remain in the liquid phase and do not dissolve in it or only insignificantly.
  • the process according to the invention makes it possible to produce a catalytically active molding in a simple and cost-effective manner.
  • the catalytic material is fixed in place in the structure of the shaped body. Ie. it is not - as in conventional such catalysts - a powder or Granulat thoroughlyung, which is subject to mechanical abrasion.
  • the proposed molded body can be produced without subsequently a catalytically active layer must be applied to structuring constituents of the shaped body. Because of the use of an additive shaping method proposed according to the invention, the shaped body can also be produced easily and inexpensively even in complicated geometries.
  • the molded article can be catalytically activated relatively quickly and easily by the selective removal of the second element after shaping.
  • the first element 5 to 99.5% by weight, preferably 60 to 98% by weight, particularly preferably 80 to 95% by weight, of the alloy are formed by the first element.
  • the first element may be formed of one of the following metals: Cu, Ni, Co, Fe, Ru.
  • the first element is basically formed from a metal which is catalytically active or catalytically activatable.
  • the second element may be formed of one of the following metals: Al, Si, Zn, Cr, Mg, Zr, Ti, V.
  • a combination of the first and second elements is always chosen so that the second element is selectively removable by means of a liquid phase so that the first element remains and forms the porous structure.
  • the alloy may contain as a third element one of the following precious metals: Ag, Pt, Pd. The alloy expediently contains at most
  • the additive forming method is selected according to an embodiment of the invention from the following group: selective electron beam melting, selective laser melting, powder or wire-based laser deposition welding.
  • an energy source is computer-guided along a predetermined path.
  • a layer formed from the powder is fused or sintered with underlying material.
  • laser deposition welding the powder is fed together with the laser beam and welded to the underlying material.
  • the liquid phase is selected from the following group: acid, base.
  • acids sulfuric acid, phosphoric acid, HCl, HF or the like can be preferably used.
  • bases for example, aqueous solutions of
  • Metal hydroxide salts especially KOH and NaOH can be used.
  • the liquid phase may be added to further elements, for example Zn or Cr.
  • the further elements cause a doping of the first element during the removal of the second element. Such doping can increase the effectiveness of the catalyst.
  • the liquid phase is contacted with the alloy for a period of 0.1 to 100 hours. If acids or bases are used as the liquid phase, these expediently have a temperature in the range between 1 and 10 ° C.
  • the shaped body is brought into contact only in predetermined sections with the liquid phase. Ie. After being brought into contact with the liquid phase, the shaped body can have further sections, which are formed from the alloy and have no surface with a porous structure.
  • the second element is removed only superficially from the alloy by contact with the liquid phase, so that first regions cover second regions, wherein the first regions have a larger pore volume than the second regions.
  • a first porosity of the first regions is an open porosity with a pore volume usually greater than 10%.
  • An average pore diameter is usually in the range of 10 nm to 100 ⁇ .
  • the second regions or the above-mentioned further sections are formed from the alloy. They have a second porosity. This is an essentially unavoidable inter- or intracrystalline porosity in the production of alloys.
  • the second porosity is a closed porosity with a pore volume of less than 10%.
  • the shaped body expediently forms a cellular structure through which a fluid can flow.
  • the cellular structure can be accommodated in a tube.
  • the molded body in one-piece construction may comprise the tube and at least one cellular structure accommodated in the tube.
  • the cellular structure may extend in a plane which intersects a tube axis of the tube.
  • several cellular structures can be added sequentially along the tube axis. Breakthroughs of a cellular structure of one plane may be staggered with respect to further breakthroughs of another cellular structure in an adjacent plane.
  • the aforementioned structures enable a particularly efficient contact between the catalytically active molded body and the fluid to be brought into contact therewith. Furthermore, by the geometry of the shaped body, in particular the cellular structure, pressure drop, heat transfer, mixing, etc. are adjusted.
  • the liquid phase is passed for contacting in sections for a predetermined time through the tube.
  • the second element can thus be separated out of the alloy separately, both in the region of the inner wall of the tube and on the surface of the cellular structure, and thus a surface with a porous structure can be produced.
  • a catalytically active molded article having a predetermined cellular structure produced by an additive molding method wherein the cellular structure is made of an alloy containing a first and a second element different from the first element and a porous one at least on its surface Having structure which is formed by selectively removing the second element by means of a liquid phase of the alloy.
  • a "cellular structure” is understood to mean a macroscopic structure which is formed from a multiplicity of cells through which a fluid can flow.
  • the cellular structure may be geometrically regular or even irregular. It may be formed as a two- or three-dimensional grid and / or have tubular passages, perforated walls or floors or the like.
  • the porous structure is open-pored.
  • a pore volume of the porous structure is suitably more than 10%.
  • the molded body is formed by selectively removing the second element from the alloy by means of the liquid phase.
  • the molded article is immediately catalytically active or it is by a further process step in a conventional manner, for. As a reduction, catalytically activated.
  • the first regions formed by the porous structure may cover second regions, wherein the first regions have a larger pore volume than the second regions.
  • the first regions form a catalytically active layer, whereas the second regions provide the structural stability of the molded article.
  • 1 is a three-dimensional, partially broken view of a shaped body
  • 2 shows a scanning electron microscope image of a first region of the molded body
  • Fig. 1 shows a three-dimensional representation of a generally designated by the reference numeral 1 shaped body.
  • the molded body 1 has cellular structures 2, which are accommodated in a tube 3.
  • the tube 3 has at its first end a first flange 4 and at its opposite second end a second flange 5. A diameter of the tube 3 widens from the first end to the second end.
  • Each cellular structure 2 here forms a plane which runs approximately perpendicular to the axis of the tube 3.
  • the cellular structure 2 has here hexagonal breakthroughs. It is made in one piece with the tube 3.
  • FIG. 2 shows a scanning electron micrograph of the surface of the cellular structure 2.
  • the surface of the cellular structure 2 is formed by a highly porous structure of copper.
  • An average pore size is about 0.3 to 0.6 ⁇ .
  • the porous surface shown in Fig. 2 may be formed in the same way on the inner wall of the tube 3.
  • FIG. 3 illustrates the method according to the invention with reference to a flowchart.
  • a powder is taken, which z. B. is formed from a CuZn10 alloy.
  • An average grain size of the powder is in the range of 45 to 105 m.
  • the shaped body 1 shown in FIG. 1 is produced by means of selective electron beam melting.
  • the selective electron beam melting process is well known to those skilled in the art.
  • the second element of the alloy formed of Zn is selectively leached by means of NaOH.
  • NaOH is passed through the pipe 3 for a predetermined time.
  • a contact time between the NaOH and the molded body 1 and a temperature are selected so that the second element of the cellular structures 2 is removed only superficially. Ie. inside the cellular structures 2, the dense alloy remains. With such cellular structures 2, a particularly good heat dissipation to the wall of the tube 3 can be achieved.
  • the surface formed essentially by the first element is either immediately catalytically active or it may be, for. B. by reduction, are activated catalytically.
  • the reduction may be accomplished, for example, by contact with hydrogen or the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un corps moulé (1) à action catalytique, le procédé comprenant les étapes consistant à : fournir une poudre produite à partir d'un alliage, l'alliage comportant un premier élément et un deuxième élément différent du premier élément, lequel deuxième élément peut être enlevé de manière sélective de l'alliage au moyen d'une phase liquide, produire le corps moulé (1) conformément à une géométrie prédéfinie à partir de la poudre au moyen d'un procédé de façonnage additif et enlever de l'alliage, de manière sélective, au moins une partie du deuxième élément à l'aide de la phase liquide, de telle sorte que le premier élément reste au moins sur une surface du corps moulé (1) et forme une structure poreuse.
PCT/EP2017/052270 2016-02-12 2017-02-02 Procédé de production d'un corps moulé à action catalytique et corps moulé à action catalytique WO2017137305A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102016202200.8 2016-02-12
DE102016202200 2016-02-12
DE102016207146.7 2016-04-27
DE102016207146.7A DE102016207146A1 (de) 2016-02-12 2016-04-27 Verfahren zur Herstellung eines katalytisch aktiven Formkörpers und katalytisch aktiver Formkörper

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WO2017137305A1 true WO2017137305A1 (fr) 2017-08-17

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DE (1) DE102016207146A1 (fr)
WO (1) WO2017137305A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021224007A1 (fr) * 2020-05-07 2021-11-11 Clariant International Ltd Procédé de production de catalyseurs à l'aide d'une technologie d'impression 3d

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998758A (en) * 1973-02-21 1976-12-21 Clyde Robert A Supported catalyst
DE4345265A1 (de) * 1993-10-16 1995-09-21 Degussa Katalysatorvorstufe für einen aktivierten Metall-Festbettkatalysator nach Raney
DE69425307T2 (de) * 1993-10-07 2000-12-14 Centre Nat Rech Scient Raney Katalysator Zusammensetzung für die Hydrogenierung von Halonitroaromatischen Verbindungen und Verfahren zur Verwendung derselben
WO2009047141A1 (fr) * 2007-10-08 2009-04-16 Basf Se Utilisation de corps façonnés dotés de propriétés catalytiques comme éléments de réacteur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998758A (en) * 1973-02-21 1976-12-21 Clyde Robert A Supported catalyst
DE69425307T2 (de) * 1993-10-07 2000-12-14 Centre Nat Rech Scient Raney Katalysator Zusammensetzung für die Hydrogenierung von Halonitroaromatischen Verbindungen und Verfahren zur Verwendung derselben
DE4345265A1 (de) * 1993-10-16 1995-09-21 Degussa Katalysatorvorstufe für einen aktivierten Metall-Festbettkatalysator nach Raney
WO2009047141A1 (fr) * 2007-10-08 2009-04-16 Basf Se Utilisation de corps façonnés dotés de propriétés catalytiques comme éléments de réacteur

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021224007A1 (fr) * 2020-05-07 2021-11-11 Clariant International Ltd Procédé de production de catalyseurs à l'aide d'une technologie d'impression 3d

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