METHOD FOR PRODUCING A CATALYST SYSTEM FOR GAS REACTIONS

Abstract

A method for producing a catalyst system for gas reactions comprising at least one planar structure of noble metal having gas-permeable openings, comprising the steps of:

(1) providing at least one noble metal powder consisting of at least substantially spherical noble metal particles, and

(2) repeatedly applying the noble metal powder or powders provided in step (1) in layers to a substrate in a build chamber, respectively followed by an at least partial melting of the respective noble metal powder applied as a layer with high-energy radiation, and allowing the melted noble metal powder to solidify within the scope of additive manufacturing.

Claims

1.-13. (canceled)

14. A method for producing a catalyst system for gas reactions comprising at least one planar structure of noble metal having gas-permeable openings, comprising the steps of: (1) providing at least one noble metal powder consisting of at least substantially spherical noble metal particles, and (2) repeatedly applying the noble metal powder or powders provided in step (1) in layers to a substrate in a build chamber, respectively followed by an at least partial melting of the respective noble metal powder applied as a layer with high-energy radiation, and allowing the melted noble metal powder to solidify within the scope of additive manufacturing, wherein the or every planar structure of noble metal comprising gas-permeable openings has an individual weight per unit area in the range of 25 to 2500 g/m.sup.2, wherein the noble metal particles of the noble metal powder or powders have a particle size distribution with a d.sub.10 value of ≥5 μm and a d.sub.90 value of ≤80 μm, and wherein the noble metal of the noble metal particles of the noble metal powder or powders is selected from the group consisting of noble metal alloys of platinum with 1-15 wt. % rhodium, platinum with 2-15 wt. % rhodium and 0.1-20 wt. % palladium, platinum with 2-15 wt. % rhodium, 0.1-20 wt. % palladium, and 0.1-2 wt. % ruthenium, platinum with 2-15 wt. % rhodium, 0.1-20 wt. % palladium, and 0.1-5 wt. % iridium, palladium with 3-15 wt. % platinum, palladium with 1-20 wt. % platinum and 1-10 wt. % rhodium, palladium with 1-25 wt. % tungsten, and palladium with 1-15 wt. % nickel.

15. The method according to claim 14, wherein at least 80% of the noble metal particles, relative to their number, satisfy the condition 0.8 ≤d.sub.min/d.sub.max ≤1.0, wherein d.sub.min is the minimum diameter and d.sub.max is the maximum diameter of an individual noble metal particle.

16. The method according to claim 14, wherein the noble metal particles are produced by an atomization process.

17. The method according to claim 14, wherein the d.sub.50 value of the particle size distribution is in the range from 20 to 30 μm.

18. The method according to claim 14, wherein the d.sub.10 value is ≥10 μm and the d.sub.90 value is ≤45 μm.

19. The method according to claim 18, wherein the d.sub.10 value is in the range of ≥10 μm to ≤20 μm, and the d.sub.90 value is in the range of ≥30 μm to ≤45 μm.

20. The method according to claim 14, wherein the catalyst system comprises or consists of one planar structure of noble metal, a plurality of identical planar structures of noble metal, or a plurality of different planar structures of noble metal, and wherein the one planar structure of noble metal, the plurality of identical planar structures of noble metal, or the plurality of different planar structures of noble metal constitute a complete catalyst system for gas reactions or a catalyst subsystem in the sense of a part of a complete catalyst system for gas reactions.

21. The method according to claim 14, wherein the planar structures of noble metal are planar objects selected from the group consisting of grids, perforated plates, screens, and nets.

22. The method according to claim 14, wherein the planar structure of noble metal or planar structures have a surface area in the range of 0.25 to 35 square meters.

23. The method according to claim 21, wherein the net or nets have a structure akin to a woven fabric, a weft knitted fabric, or a warp knitted fabric.

24. The method according to claim 23, wherein the structure of the net is as if it were based on round wire and/or on wire with a cross-sectional shape other than round.

25. The method according to claim 24, wherein, independently of the cross-sectional shape, the wire cross-sectional area ranges from 400 to 22500 μm.sup.2.

26. The method according to claim 14, wherein the selection of digital 3D design data within the context of additive manufacturing influences surface roughness, porosity, and/or solidity of the noble metal material of the noble metal planar formation or planar formations.

Description

[0044] In one embodiment of the method according to the invention, only one noble metal powder or, respectively, only one type of noble metal powder is provided in step (1), and the catalyst system is consequently manufactured additively from a single noble metal alloy. In this embodiment, unmelted noble metal powder can be recovered according to type and, if applicable, be reused directly. Here, the catalyst system produced via additive manufacturing in the method according to the invention consists of the corresponding noble metal alloy.

[0045] In other embodiments of the method according to the invention, several types of noble metal powder which differ from one another with respect to the alloy composition are provided in step (1), and the catalyst system is consequently manufactured additively from several different of the aforementioned metal alloys, or consists thereof after completion of additive manufacturing. Here, unmelted noble metal powder is not recovered according to type, i.e., but as a mixture of different noble metal powders which can be supplied to conventional noble metal recycling. Here, the catalyst system produced by additive manufacturing in the method according to the invention consists partially of a first noble metal alloy and partially of at least one noble metal alloy differing therefrom. This may mean, for example, that the catalyst system comprises multiple planar structures of noble metal having multiple gas-permeable openings, wherein the individual planar structures of noble metal do not all consist of the same noble metal alloy. For example, the individual planar structures of noble metal may consist at least partially of noble metal alloys that differ from one another, for example respectively of a different noble metal alloy. Different noble metal alloys may also be processed within a single planar structure of noble metal.

[0046] The actual additive manufacturing takes place during step (2), in particular as a 3D printing method. Digital 3D design data of the catalyst system are hereby used, for example in the form of CAD data or data formats of the relevant 3D printing system manufacturer. Various structural features of the catalyst system or, respectively, of the planar structures of noble metal comprised thereof and having at least one gas-permeable opening can be determined via the selection of the digital 3D design data, as will be explained subsequently.

[0047] In step (2), the noble metal powder or powders provided in step (1) are repeatedly applied in layers to a substrate in a build chamber, respectively followed by at least a partial melting of the respective noble metal powder applied as a layer with high-energy radiation and allowing the melted noble metal powder to solidify within the scope of an additive manufacturing. The number of repetitions naturally depends on the type and size of the catalyst system to be produced in the method according to the invention.

[0048] Usually, the build chamber is first evacuated or filled with an inert gas (for example, nitrogen or a noble gas).

[0049] The high-energy radiation can be laser or electron beams, for example. In particular, near-infrared lasers with a wavelength in the range of 1040 to 1080 nm are suitable as lasers. A 3D laser printer is preferably used; its laser spot can expediently have a diameter in the range of 10 μm to 150 μm.

[0050] At the end of the process, free or loose unmelted noble metal powder can be removed from the component, i.e. from the catalyst system.

[0051] In the method according to the invention, a catalyst system for gas reactions comprising at least one planar structure of noble metal having gas-permeable openings is produced. The catalyst system for gas reactions may comprise or consist of one planar structure of noble metal, a plurality of identical planar structures of noble metal, or a plurality of different planar structures of noble metal. “A plurality of different planar structures of noble metal ” may mean that variability exists in the type of noble metal alloys and/or in structural features. The one planar structure of noble metal, the plurality of identical planar structures of noble metal, or the plurality of different planar structures of noble metal may constitute a complete catalyst system for gas reactions, or a catalyst subsystem in the sense of a part of a complete catalyst system for gas reactions. For example, it may be a single net layer or a net package of two or more net layers, for example up to 40 net layers.

[0052] The individual planar structure of noble metal or planar structures produced as a catalyst system or part thereof in the method according to the invention have a weight by unit area in the range of 25 to 2500 g/m.sup.2 or in the range of 75 to 1000 g/m.sup.2, for example.

[0053] A planar structure of noble metal having gas-permeable openings within the meaning of the present invention may, for example, respectively be planar (non-curved) objects, such as grids, perforated plates, screens, or preferably nets (individual net layers). The planar structure of noble metal may have a superficial extent of up to several square meters, for example in the range of 0.25 to 35 square meters; if circular in shape, the diameter of the planar structure of noble metal may be up to 6.5 meters, for example. When the planar structure of noble metal is viewed from above, the entirety of the gas-permeable openings within a single planar structure of noble metal usually forms a uniform, regularly repeating pattern. Likewise, when the planar structure of noble metal is viewed from above, adjacent gas-permeable openings or net meshes have a uniform or variable edge distance formed by the noble metal, for example in the range of 30 to 200 μm. In each instance, when the planar structure of noble metal is viewed from above, patterns, edge distance, size, and also the shape of the openings are structural features which can be determined by the selection of aforementioned digital 3D design data.

[0054] In a preferred embodiment of a planar structure of noble metal in the form of a net having gas-permeable openings produced by the method according to the invention, said planar structure of noble metal may have, for example, a structure akin to a woven fabric, or a weft or warp knitted fabric. In particular, the nets thereby represent the gas-permeable openings. The structure of the net can thereby be as if it were based on wire with a round cross-sectional shape, i.e. a round wire. However, it is also possible to design the structure of the net as if it were based on wire with a cross-sectional shape that is other than round, i.e., for example, elliptical, rectangular, square, or hexagonal. Independently of the cross-sectional shape, the wire cross-sectional area can, for example, be in the range of 400 to 22500 μm.sup.2. In the event of round wire, the cross-section can be determined by a diameter, for example, in the range of 30 μm to 150 μm; for example, the instance of a round wire having a diameter of 30 μm corresponds to a weight by unit area at the lower end of the aforementioned ranges of 25 to 2500 g/m.sup.2 or of 75 to 1000 g/m.sup.2, respectively. Both the type of net structure, the cross-sectional shape, and the cross-sectional area are structural features that can be determined by the selection of the digital 3D design data. For example, a net structure can also be created as if it were based not only on one wire type but rather on two or more wires respectively having different cross-sections with respect to cross-sectional shape and/or cross-sectional area.

[0055] Furthermore, within the context of additive manufacturing, the selection of digital 3D design data can influence properties such as surface roughness, porosity, and/or solidity of the noble metal material of the planar structure of noble metal or planar structures having gas-permeable openings. The surface of the noble metal material may thus be more or less rough; the noble metal material may be pore-free or more or less porous. As of a certain cross-section of the noble metal material, the latter may also be hollow on the inside.

[0056] As follows from the aforementioned, the method according to the invention allows a flexible production of a catalyst system for gas reactions comprising at least one planar structure of noble metal having gas-permeable openings, optionally having structural features which cannot be realized by means of conventional production methods of the prior art (knitting, interlacing, weaving). For example, a structure optimized in terms of flow mechanics can be produced.

[0057] It is particularly to be emphasized that the method according to the invention also makes it possible to realize a highly catalytically active surface of a relevant catalyst system with, at the same time, minimal use of noble metal, if so desired. In addition to the aforementioned influence on aforementioned structural features of the catalyst system, the digital 3D design data used in step (2) within the framework of actual additive manufacturing can be selected such that a catalyst system with an economically efficient ratio of noble metal use to highly catalytically active surface is developed. In other words, a savings of noble metal can be achieved as compared to the production of a corresponding catalyst system by means of conventional production methods of the prior art (weft knitting, warp knitting, weaving).

Exemplary Embodiment

[0058] To produce a catalyst system according to the invention, a noble metal powder comprising PtRh5 was used. The powder was produced by inductive melting of the starting material and gas atomization (EIGA “electrode induction-melting gas atomization”) using argon as an inert gas. Spherical particles were obtained. The obtained noble metal powder was sorted by screening (Retsch AS 200).

[0059] The particle size distribution in the form of a mass distribution cumulative curve was determined by laser diffraction. The sorted powder had a d.sub.10 of 12.6 μm, a d.sub.50 of 24.1 μm, and a d.sub.90 value of 42.3 μm.

[0060] A circular shaped catalyst system, consisting of 6 net planes having gas-permeable rectangular openings of the dimensions 405 μm−145 μm and formed by 120 μm-wide webs, was produced from said powder in an additive manufacturing process by selective laser melting at a system of the company Trumpf, model T1000. The dimensions were determined using REM images. The 6 net planes were connected to one another via webs. The weight by unit area of each individual layer corresponded to 955 g/m2.