Catalytically active product, method for producing such product, and reactor containing the product

Abstract

A method for producing a catalytically active product (10) is disclosed. The method includes depositing a thermite or thermate composition (28) on a substrate, heating the substrate (11) with the composition (28) to initiate a thermite reaction and adhere a layer of a first metal (27) to the substrate, removing oxides of a second metal (29), and forming a roughened surface of the layer of first metal. A ceramic material is then deposited on the roughened surface of the first metal (27) to form a ceramic layer (14) comprising catalytically active material (16) thereon. The catalytically active product (10) and a reactor (22) comprising a plurality of laminated sheets of the catalytically active product (10) are also disclosed.

Description

Technical Field

[0001] The present invention relates to a catalytic active product and a method for producing the same. The catalytic active product is used in various chemical reactions including combustion, purification, catalytic reforming, etc. For example, the catalytic active product is used for the purification of flue gas related to hydrocarbons such as carbon monoxide and / or VOC and PAH. Such a catalytic active product can be used in a reactor for various types of chemical reactions. This type of catalytic active product can also be used in a burner for the combustion of gas fuels such as natural gas, propane, butylene or similar gases. The present invention also relates to a reactor containing such a catalytic active product.

Background Art

[0002] Multiple different types of catalytic devices are known in the prior art. One type of catalytic device is disclosed in Patent Document 1. Patent Document 1 describes a catalyst and a method for producing the same, in which a layer of porous ceramic is formed on a mesh substrate by thermal spraying, and then the surface area of the ceramic layer is enlarged, and thereafter, the surface area enlarged ceramic layer is impregnated with a catalytic active material. The purification results and production methods of this known catalyst are sufficient in many applications, but there is room for improvement in both the method for producing the catalytic active product and the catalytic active product itself.

[0003] One problem with the prior art methods for producing catalytic active products is that they are complex and require expensive equipment.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The object of the present invention is to overcome or at least mitigate one or more of the problems described above in relation to the prior art, to provide an efficient method for producing catalytically active products, and to provide such products that enable easy production. [Means for solving the problem]

[0006] The present invention relates to a method for producing a catalytically active product, wherein the method is: a) The step of providing a substrate, b) A step of depositing a thermite or thermate composition onto the substrate, wherein the composition comprises at least a first metal oxide and a second metal powder. c) Heating the substrate having the composition to a temperature at which the oxide of the first metal is reduced to the first metal in an exothermic reaction, thereby oxidizing the second metal to an oxide of the second metal, and thereby bonding the first metal to the substrate by the heat from the reaction, d) a step of removing the oxide of the second metal, thereby forming a layer of the first metal on the substrate, wherein the layer has a rough surface, e) A step of depositing a ceramic material on the rough surface of the first metal to form a ceramic layer thereon, f) The step of adding a catalytically active material to the ceramic layer, Includes.

[0007] The method according to the present invention makes it possible to easily and efficiently produce catalytically active products. The present invention allows for the production of catalytically active products without a thermal spraying process. By using a thermite or thermate composition, safe, reliable, and efficient fixation to the substrate becomes possible in subsequent steps for the production of catalytically active products, while forming a rough surface for reliable and efficient fixation of the ceramic layer.

[0008] A thermite composition is a pyrotechnic composition of metal powder and metal oxide. When ignited by heat, the thermite composition undergoes an exothermic oxidation-reduction reaction. The thermite composition is found to efficiently adhere to a substrate, such as a metal substrate in the form of a mesh or plate material of steel or other suitable metal, by bonding to the substrate due to the heat generated during the thermite reaction, while a rough surface can be efficiently achieved by removing the resulting metal oxide and other residual products by washing or other suitable processes. The oxide of the first metal in the composition may be a transition metal oxide. The second metal in the composition may be an alkaline earth metal or a transition metal that oxidizes more easily than the first metal. For example, the second metal is aluminum.

[0009] The thermite composition is a thermite composition enriched with a salt-based oxidizing agent, such as a nitrate or peroxide. Furthermore, other materials such as graphite may be used. Therefore, thermite or thermite composition may contain graphite.

[0010] The method may include the step of providing a thermite or thermite composition as a suspension. Thus, the thermite or thermite composition can be deposited onto a substrate in an efficient manner by spraying or other coating processes, and the suspension can be deposited at any suitable temperature, such as room temperature. After a heating process to initiate the redox reaction of the composition, an adhesion layer for subsequent fixation of the ceramic layer is efficiently formed.

[0011] After fixing a first metal layer to a substrate by thermite bonding such as welding, the method may include a step of providing a ceramic material as a suspension and depositing a ceramic layer on the first metal layer, for example by spraying the suspension. Thus, the ceramic material is easily formed, and the rough surface of the first metal layer is mechanically and reliably fixed to the substrate by, for example, drying and firing.

[0012] Furthermore, the present invention relates to catalytically active products produced by the above method.

[0013] The present invention also relates to a catalytic reactor comprising a central axis and a stack of catalytically active sheets, wherein the catalytically active sheets are stacked in the axial direction, and each of the catalytically active sheets is formed from a catalytically active product produced by the above method.

[0014] The catalytic reactor may have a central opening, and at least some of the catalytically active sheets may have axially extending flanges at least partially positioned around the central opening, with the flange of one catalytically active sheet extending into the opening of an adjacent catalytically active sheet. By combining the central opening and the flanges of the catalytically active sheets, it is possible to guide the first reactant axially along the stack and to distribute the first reactant radially along the catalytically active sheets to react with a second reactant, which is guided axially, for example, at a position radially outside the central opening. Thus, the present invention provides an efficient reactor in which the concentration of the first reactant is higher near the central opening and lower towards the radially outward direction. In this way, the reactor is flexible and can be used for different types of reactions and adapted to different process parameters. For example, the catalytic reactor can be used for combustion, catalytic partial oxidation, catalytic reforming, autothermal reforming, hydrogenation, selective oxidation, etc. The reactor structure allows for efficient use of the catalytically active material in the catalytically active sheets. For example, the first reactant may be a fuel such as a mixture of gaseous fuels in the form of a biofuel, and the second reactant may be air or oxygen, and an efficient reactor for the combustion of such a mixture of fuels can be achieved.

[0015] Each catalytic sheet may have a radially extending portion that extends radially from a central opening. The radially extending portion of one catalytic sheet may be positioned with a gap between it and the radially extending portions of adjacent catalytic sheets. Thus, the first reactant can be distributed into the gap along the radially extending portion of the catalytic sheet for efficient reaction with the second reactant.

[0016] The flange may taper towards its free end, and the catalytically active sheets can be laminated in an efficient manner, for example, by providing gaps between the radially extending portions of adjacent catalytically active sheets.

[0017] The catalytically active sheet may be arranged in a mesh structure such as wire mesh, perforated plate material, or expanded metal, where the first reactant can be guided axially through the stack by cooperating flanges, while some of the first reactant is guided radially through the flanges in a balanced manner by openings in the mesh structure. The flanges and radially extending portions may be formed in the mesh structure. Thus, the second reactant can be efficiently guided axially through the radially extending portions of the stack. For example, the entire catalytically active sheet may be formed in the mesh structure.

[0018] Alternatively, the catalytically active sheet may be formed from a plate material such as sheet metal, the flange may have holes, and / or the radially extending portion may have through-apers distributed around the central opening. Thus, the first reactant can be guided axially through the stack by the cooperating flanges, while some of the first reactant is guided radially through the flange in a balanced manner by the holes in the flange. The second reactant can be efficiently guided axially through the radially extending portion of the stack by the aperture to react with the first reactant guided radially outward into the gap along the radially extending portion.

[0019] The stack of catalytically active sheets, or at least the central opening, may be sealed at one end. At the end opposite to the end where the first reactant is introduced, by sealing the central opening or the stack, the first reactant within the stack is efficiently distributed. The first reactant is guided axially through the stack by cooperating flanges, and by sealing the ends, the first reactant is pushed radially.

[0020] The catalytically active sheet may comprise a substrate and a ceramic layer adhered to the substrate, and pores provided with a catalytically active material are formed in the ceramic layer.

[0021] Also, the catalytically active sheet may include a thermite composition and a layer of a first metal formed from the removal of an oxide of a second metal after a redox reaction, and the ceramic layer is adhered to the substrate through the layer of the first metal and its rough surface protruding into the ceramic layer. In this way, the ceramic layer containing the catalytically active material is efficiently adhered to a substrate such as a mesh structure or a plate.

[0022] The catalytic reactor may comprise a reaction vessel having an inlet for a first reactant, at least one inlet for a second reactant, and at least one outlet, and the stack of catalytically active sheets is disposed within the reaction vessel, the inlet for the first reactant is disposed at one end of the stack and is aligned with the central opening of the catalytically active sheet, and at least the central opening is sealed at the end opposite to the stack.

[0023] A method of providing a catalytic reaction is also disclosed, the method comprising a) supplying a first reactant axially into the central opening of one of the catalytically active sheets of a stack of catalytically active sheets; b) guiding some of the first reactant at least partially around some of the openings and axially through axially extending flanges extending axially within the central openings of adjacent catalytically active sheets; c) guiding some of the first reactant radially outward from the flange and contacting it with a second reactant to provide the catalytic reaction; comprising.

[0024] An alternative method for manufacturing a catalytically active sheet is also disclosed, the method comprising: a) providing a substrate; b) depositing particles of a first material and a second material on the substrate, the particles of the second material having a higher melting point than the first material; c) adhering the first material and the particles to the substrate by heating the substrate having the first material and the particles to a temperature at which the first material is melted and the particles of the second material are not melted, the particles being partially embedded in the first material and forming a rough surface; d) depositing a ceramic material on the rough surface to form a ceramic layer thereon; e) adding a catalytically active material to the ceramic layer; comprising.

[0025] The manufacturing method of the catalytically active sheet enables the easy and efficient production of the catalytically active sheet. By this manufacturing method, the catalytically active sheet can be produced without going through a thermal spraying process. By combining the first material and the particles, a safe, reliable and efficient fixing of the ceramic layer to the substrate for manufacturing the catalytically active sheet becomes possible.

[0026] The method may include the step of providing particles of a first material and / or a second material as one or more suspensions, and optionally, both together as a suspension. Thus, the first material and / or the second material can be deposited on a substrate in an efficient manner by spraying or other coating processes, and the suspensions can be deposited at any suitable temperature, such as room temperature. Thus, the first material can be deposited on the substrate without first melting. The method may then include the step of heating the substrate having particles of the first and second materials thereon in a furnace such as a vacuum furnace, or using a reducing gas or an inert gas, in order to melt only the first material and bond the first material to the substrate while fixing the particles to the first material. Thus, the first material and particles can be manufactured in an efficient and reliable manner, and an adhesive layer for subsequent fixing of the ceramic layer can be efficiently formed.

[0027] After fixing the first material to the substrate by melting it, the method may include the step of providing a ceramic material as a suspension and depositing a ceramic layer by depositing the suspension onto the first material containing particles, for example by spraying. Thus, the ceramic material is formed in an easy manner, partially surrounding the particles protruding from the first material, and the ceramic layer is mechanically and securely fixed to the substrate by, for example, drying and firing.

[0028] Further features and advantages of the present invention will become apparent from the following description of embodiments, the accompanying drawings and dependent claims. [Brief explanation of the drawing]

[0029] As an example, embodiments of the present invention will be described below with reference to the attached drawings.

[0030] [Figure 1] This is an enlarged schematic cross-sectional view of a portion of the catalytically active product according to one embodiment. [Figure 2] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 1 according to the first embodiment. [Figure 3] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 1 according to the first embodiment. [Figure 4] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 1 according to the first embodiment. [Figure 5] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 1 according to the first embodiment. [Figure 6] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 1 according to the first embodiment. [Figure 7] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product according to a second embodiment. [Figure 8] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product according to a second embodiment. [Figure 9] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product according to a second embodiment. [Figure 10] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product according to a second embodiment. [Figure 11] Figure 1 shows a series of schematic cross-sectional views of a method for producing the catalytically active product according to a second embodiment. [Figure 12] This is a schematic diagram of a catalytically active product in the form of a sheet according to one embodiment, in which the catalytically active sheet is arranged with flanges and arranged in the form of a mesh. [Figure 13] Figure 12 is a schematic side view of the catalytically active sheet. [Figure 14] Figure 12 is a schematic side view of the stack of catalytically active sheets. [Figure 15] This is a schematic diagram of a catalytically active sheet according to another embodiment, which is in the form of a plate having an aperture and holes in the flange. [Figure 16] Figure 15 is a schematic side view of the catalytically active sheet. [Figure 17] Figure 15 is a schematic side view of the stack of catalytically active sheets. [Figure 18]This is a schematic cross-sectional view of a catalytic reactor according to the first embodiment of the present invention. [Figure 19] Figure 18 is a schematic cross-sectional view of a catalytic reactor, showing the flow of reactants and products within the reactor. [Figure 20] This is a schematic cross-sectional view of a catalytic reactor according to a second embodiment of the present invention. [Figure 21] Figure 20 is a schematic cross-sectional view of a catalytic reactor, showing the flow of reactants and products within the reactor. [Figure 22] This is an enlarged schematic cross-sectional view of a portion of the catalytically active product according to another embodiment of the present invention. [Figure 23] Figure 22 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 22 according to one embodiment. [Figure 24] Figure 22 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 22 according to one embodiment. [Figure 25] Figure 22 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 22 according to one embodiment. [Figure 26] Figure 22 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 22 according to one embodiment. [Figure 27] Figure 22 shows a series of schematic cross-sectional views of a method for producing the catalytically active product shown in Figure 22 according to one embodiment. [Modes for carrying out the invention]

[0031] With respect to Figure 1, the catalytically active product 10 according to the present invention is schematically shown. The catalytically active product 10 is configured to be used to accelerate a chemical reaction. For example, the catalytically active product 10 is arranged for combustion, purification, catalytic reforming, etc. For example, the catalytically active product 10 is arranged to purify flue gas with respect to carbon monoxide and / or hydrocarbons such as VOCs and PAHs. For example, the catalytically active product 10 may be part of a reactor and arranged in a reaction vessel for a chemical reaction, as described below. For example, the catalytically active product 10 is included in a reactor for the combustion of gaseous fuels such as natural gas, propane, butylene or similar gases or mixtures of different fuels, for heating purposes.

[0032] The catalytically active product 10 includes a substrate 11, a first material 12, particles 13 of a second material, a ceramic layer 14 containing a ceramic material having pores 15, and a catalytically active material 16. The first material 12 and particles 13 form an adhesion layer on the substrate 11. For example, the first material 12 is placed directly on the substrate 11, and the particles 13 are partially embedded within the first material 12 and protrude from its surface. The ceramic layer 14 is placed on top of the adhesion layer formed by the first material 12 and particles 13, and the ceramic layer 14 engages with the particles 13. Thus, the adhesion layer formed by the first material 12 and particles 13 is located between the substrate 11 and the ceramic layer 14.

[0033] According to one embodiment, the catalytically active product 10 is formed as a sheet, for example, in the form of a mesh structure, i.e., a sheet having a plurality of through holes. For example, the substrate 11 is formed as a wire mesh, grid, etc. Alternatively, the substrate 11, and therefore the catalytically active product 10, may also be formed as a sheet in the form of a plate material with holes, which will be described in more detail below. For example, the substrate 11 is a metal or an alloy, or contains a metal or an alloy. According to one embodiment, the substrate is made of steel such as stainless steel, aluminum, or copper. Alternatively, the substrate 11 is made of a polymer material such as polytetrafluoroethylene or a similar polymer, or a composite material, which can withstand relatively high temperatures. In general, the substrate 11 should be able to withstand temperatures of at least 350°C. In some cases, it should be able to withstand temperatures far above this level, such as at least 500°C, at least 700°C, or at least 900°C.

[0034] A first material 12 is placed on a substrate 11 that forms the basic structure. The substrate 11, or at least a portion or side thereof, is coated with the first material 12. In the illustrated embodiment, the top surface of the substrate 11 is coated with the first material 12. Alternatively, both sides, all or the entire surface of the substrate 11 is coated with the first material 12. For example, the first material 12 is a metal or an alloy. For example, the first material 12 is Al or a similar metal having a relatively low melting point. Alternatively, the first material 12 is an alloy containing a metal such as Ni, Cu, Fe and / or steel and a melting point depressant.

[0035] The particles 13 are partially embedded in the first material 12 and at least partially protrude away from the substrate 11. The particles 13 are made from or include a second material having a higher melting point than the first material 12. For example, the solidus temperature of the particles 13 of the second material is higher than the liquidus temperature of the first material 12. For example, the particles 13 of the second material include metal powder, ceramic powder, or a mixture thereof. The particles 13 may have different shapes and sizes. The particles 13 are provided in or on the first material 12 to add surface roughness that helps in the adhesion of the ceramic layer 14. For example, the particles 13 have a particle size of at least 10 μm, or at least 20 μm, for example, 20 to 100 μm. For example, the second material has a porosity of at least 30%.

[0036] The ceramic layer 14 is provided on an adhesion layer formed by the first material 12 and particles 13, and is fixed thereto by the particles 13. Thus, the particles 13 are partially embedded in the first material 12 and partially embedded in the ceramic layer 14, mechanically fixing the ceramic layer 14 to the substrate 11. Thus, the ceramic layer 14 is positioned on the first material 12 and the particles 13 protruding therefrom. The ceramic layer 14 may contain alumina, zirconia, titanium dioxide, silica, tungsten carbide, silicon nitride, or similar ceramics, or mixtures thereof. The ceramic layer 14 has pores 15 formed therein, which increases the surface area for depositing the catalytically active material 16. Thus, the ceramic layer 14 is provided with the catalytically active material 16, which is positioned within its pores 15. For example, the catalytically active material 16 is a noble metal, a transition metal, or a mixture or oxide thereof. For example, the catalytically active material 16 is palladium.

[0037] Referring also to Figures 2 to 6, a method for producing the catalytically active product 10 is schematically illustrated in a series of figures according to a first embodiment. The substrate 11 is described above and schematically shown in Figure 2. The substrate 11 is coated with the first material 12 by, for example, a spraying process. The substrate 11 having the first material 12 is shown in Figure 3, and the first material 12 is provided as a layer on the substrate 11. According to one embodiment, the first material 12 is provided as a suspension, and the first material 12 is provided as particles dispersed in a liquid such as water. For example, the substrate 11 is coated with the first material 12 by a spraying process, and the first material 12 is sprayed onto the substrate 11, for example, at room temperature. Thus, the first material 12 is not heated and is not sprayed at high temperatures. Alternatively, the first material 12 is applied onto the substrate 11 by another coating process such as painting or dipping. Alternatively, the first material 12 is provided as a paste, and the paste is applied onto the substrate 11 by spreading it on the surface of the substrate 11. After applying the first material to the substrate, the substrate 11 having the first material 12 is optionally dried, for example, by heat treatment in an oven.

[0038] After coating the substrate 11 with the first material 12, particles 13 containing the second material are provided on the first material 12, as shown in Figure 4. For example, the particles 13 are provided as a suspension, also called a slurry, and the particles 13 are suspended in a liquid such as water. The suspension of particles 13 is applied onto the first material 12 supported by the substrate 11. For example, the particles 13 are applied onto the first material 12 by a spraying process, and the suspension containing particles 13 is sprayed onto the first material 12. Thus, the particles 13 may be sprayed onto the first material 12 at room temperature. After applying the particles 13 onto the first material 12, the substrate 11 supporting the first material 12 and particles 13 may be dried, for example, in an oven. Then, the substrate 11 having the first material 12 and particles 13 is heat-treated, for example, in a furnace, to a temperature that melts the first material 12 but does not melt the particles 13 of the second material. The substrate 11 is also not melted. Therefore, the first material 12 is fixed to the substrate 11 by melting it while fixing the particles 13 to the first material 12. The particles 13 are mechanically fixed to the first material 12 and are partially embedded in the first material 12 after it melts. The first material 12 is also mechanically bonded to the substrate by melting into the roughness of its surface. The particles 13 partially embedded in the first material 12 and protruding from there are shown in Figure 4. For example, the heat treatment for melting the first material 12 is carried out under vacuum in a vacuum furnace. Alternatively, the heat treatment for melting the first material 12 is carried out in a furnace using a reducing gas or an inert gas.

[0039] Next, the substrate 11 supporting the first material 12 and particles 13 comprises a ceramic layer 14 as shown in Figure 5, and the ceramic layer 14 is provided on the particles 13 and the first material 12, so that the first material 12 is positioned between the ceramic layer 14 and the substrate 11. For example, the ceramic layer 14 is deposited on the adhesion layer 12 as a slurry, such as in the form of an aqueous suspension. The ceramic layer 14 may also contain a pore-forming agent provided to form a porous structure in the ceramic material. Typically, the thickness of the ceramic layer is in the range of 0.1 to 0.8 mm, preferably in the range of 0.2 to 0.5 mm. The surface of the ceramic layer 14 is enlarged by pores 15, and the pores are configured to hold the catalytically active material 16 as shown in Figure 6.

[0040] The ceramic layer 14 may be manufactured by one of the following processes: 1) direct spraying with secondary surface area expansion by precipitation, or 2) spraying with simultaneous deposition of ceramic powder, or a combination of methods 1) and 2), followed by coating with a catalytically active material 16 through an impregnation process. Alternatively, the pore-forming agent may be a flammable material that can be burned by heat treatment. Optionally, the pore-forming agent may be a pore-forming polymer material. Alternatively, the ceramic layer 14 is a ceramic powder containing particles with a high specific surface area. For example, pores 15 are formed in the ceramic layer 14 by conventional methods.

[0041] The pores 15 of the ceramic layer 14 are configured to support the catalytically active material 16. For example, the pores 15 may be cylindrical in shape. In this way, the purified chemical can easily reach the catalytically active material 16 of the catalytically active product 10. The catalytically active material 16 may be deposited in the pores 15 of the ceramic layer by, for example, a conventional impregnation process. During impregnation, the structure of the pores 15 of the ceramic layer 14 is saturated with, for example, a solution containing the catalytically active material 16. The catalytically active material 16 may include noble metals, transition metals, or a combination thereof.

[0042] An alternative embodiment of the present invention will be described with reference to Figures 7 to 11, in which the substrate 11 is coated with a mixture of a first material and particles 13 of a second material. A substrate 11 having a mixture of a first material 12 and particles 13 is shown in Figure 7. For example, the first material 12 may also be provided as particles, and the first material 12 and the particles 13 of the second material may be provided as a mixture in a slurry. The slurry containing both the first material 12 and the particles 13 of the second material is applied onto the substrate 11, for example, by spraying, as described above. Thus, the slurry may be provided onto the substrate by spraying at room temperature. The substrate 11 containing the slurry is then optionally dried. After coating the substrate 11 with the mixture of the first material 12 and particles 13, heating is performed to melt the first material 12, but not the substrate 11 or the second material, and as shown in Figure 8, the particles 13 adhere to the first material 12, and the first material 12 adheres to the substrate 11. Therefore, the particles 13 are partially embedded in the first material 12 and protrude therefrom in a direction away from the substrate 11, obtaining a rough outer surface for fixing the ceramic layer 14 as described above. Next, the ceramic layer 14, which may be provided as a slurry, is deposited on the first material 12 and particles 13, as shown in Figure 9. For example, the ceramic layer may be deposited by spraying, as described above. Next, the ceramic layer 14 may be subjected to a surface area expansion treatment to form pores 15, as shown in Figure 10. For example, the ceramic layer 14 contains a pore-forming agent. Finally, the catalytically active material 16 is deposited, for example, by impregnation. The catalytically active material 16 may be deposited on the surface of the ceramic layer 14 and inside its pores 15.

[0043] The particles are provided in the first material 12 to add surface roughness that helps in the adhesion of the ceramic layer 14 that is subsequently placed. In other words, by providing rough particles in the first material 12, an increase in surface area can be achieved to improve the adhesion of the ceramic material 14 to the substrate 11. When heated, the first material 12 fuses to the substrate 11, and the contained particles 13 are exposed. By exposing the particles 13, the ceramic layer 14 can be fixed to the substrate 11. This is due to the increased surface area and roughness provided by the particles 13.

[0044] Referring to Figures 12 and 13, the catalytically active product 10 is schematically shown in the form of a sheet according to one embodiment of the present invention, and Figure 14 shows a stack of such catalytically active sheets 10. Although Figure 14 shows four identical catalytically active sheets 10, the stack may contain any preferred number of catalytically active sheets 10 and they do not need to be identical. For example, the catalytically active sheet 10 is arranged comprising at least a substrate 11 and a catalytically active material 16, and optionally comprising one or more of a ceramic layer 14, a first material 12, and a second material 13. For example, the catalytically active sheet 10 is arranged as described above with reference to Figure 1.

[0045] The catalytically active sheet 10 is arranged to have an axis A, a through-central opening 17, a central flange 18 that is at least partially positioned around the central opening 17 and at least partially extending axially, and a radially extending portion 19. In the illustrated embodiment, the central opening 17 is circular. Alternatively, the central opening 17 may be elliptical or rectangular, or formed in another suitable shape. In the illustrated embodiment, the flange 18 is continuous and surrounds the entire circumference of the central opening 17. Alternatively, the flange 18 may be interrupted or positioned as two or more tabs distributed around the central opening 17.

[0046] Referring particularly to Figures 13 and 14, the flange 18 extends axially, and the radially extending portion 19 extends radially from the base of the flange 18. For example, the base of the flange 18 is connected to the radially extending portion 19 and terminates at a free end. For example, the base and / or free end of the flange 18 is annular with a circular cross-section, but the flange 18 or at least its base may have a shape corresponding to another shape of the central opening 17. At least a portion of the flange 18 can be inserted into the flange 18 of an adjacent catalytic sheet 10, as shown in Figure 14. For example, the flange 18 tapers towards its free end, and the free end of the flange 18 can be inserted into the base of the flange 18 of an adjacent catalytic sheet. Therefore, the diameter or cross-sectional area of ​​the base of the flange 18 is larger than that of its free end. For example, the flange 18 is conical, more specifically frustoconical.

[0047] In the illustrated embodiment, the radially extending portion 19 extends radially from the base of the flange 18. For example, the radially extending portion 19 is a sheet or sheet portion having a central opening 17. For example, the radially extending portion 19 extends from the central opening 17 to the periphery of the catalytically active sheet 10, is a free end, and the outer circumference of the radially extending portion 19 also forms a free outer circumference where there is no catalytically active sheet 10. In the illustrated embodiment, the radially extending portion 19 is flat, extends only radially, and is perpendicular to axis A over its entire length. Alternatively, the radially extending portion 19 extends partially radially, is inclined with respect to axis A, and tapers toward the central opening 17. Alternatively, the radially extending portion 19 is formed in various structures such as depressions, corrugations, or the like, and can be optionally adapted to a similar shape of adjacent catalytically active sheets 10. Thus, the catalytically active sheets 10 are stackable. For example, as shown in Figure 14, the catalytically active sheets 10 are formed such that the flanges 18 contact each other when laminated and the radially extending portions 19 are arranged with gaps between them. For example, the catalytically active sheets 10 are laminated and then pressed together. In the embodiments shown in Figures 12-14, the catalytically active sheets 10 are arranged in a mesh structure such as a wire mesh, net or grid structure, perforated sheet or expanded metal sheet. For example, the mesh openings are 2 mm or less, for example, 0.1 to 2 mm.

[0048] In the illustrated embodiment, all catalytically active sheets 10 in the stack are arranged with flanges 18. Alternatively, at least some of the catalytically active sheets 10 have axially extending flanges 18, and the flange 18 of one catalytically active sheet extends into the central opening 17 of an adjacent catalytically active sheet 10. For example, all other catalytically active sheets 10 in the stack of sheets have flanges 18. For example, the flanges 18 cooperate to form a central tube running through the stack.

[0049] Referring to Figures 15 and 16, a catalytically active sheet 10 according to another embodiment of the present invention is schematically shown, and Figure 17 shows a stack of such catalytically active sheets 10. The catalytically active sheets 10 according to Figures 15-17 differ from the catalytically active sheets of Figures 12-14 in that they are formed from a continuous sheet such as sheet metal or other suitable sheet material, rather than being formed in a mesh structure. The catalytically active sheet 10 is arranged together with an axis A, a through-central opening 17, a central flange 18, and a radially extending portion 19. In the embodiments of Figures 15-17, the axially extending flange 18 forms a conduit as seen in Figure 17. Thus, each flange 18 is provided with through-holes 20, such as at least two, or at least four or six holes 20, which are distributed around the flange 18 and connected to the conduit formed by the flange 18 and the space formed by the gap between the radially extending portion 19. Furthermore, the radially extending portion 19 is arranged with through-apertures 21, such as at least two, four, or six through-apertures 21 distributed around the central opening 17. In Figure 16, two apertures 21 are shown by dashed lines. For example, the through-apertures 21 are positioned between the central opening 17 and the periphery of the radially extending portion 19. For example, the apertures 21 of adjacent catalytic active sheets 10 are aligned. In the illustrated embodiment, the apertures 21 are distributed around the central opening 17, similar to the holes 20, and the apertures 21 and holes 20 are positioned at the same radial angle with respect to axis A. For example, the extension of the central axis of a hole 20 intersects the corresponding extension of the central axis of an aperture 21. The apertures 21 are positioned to provide axial flow, and the holes 20 are positioned to provide substantially radial flow. For example, the holes 20 are positioned so that the radial flow intersects the axial flow passing through the apertures 21. In the illustrated embodiment, the aperture 21 extends in the radial plane. Optionally, the aperture 21 is larger than the hole 20. In the drawing, the aperture 21 and hole 20 are circular, but they may have other shapes such as elliptical, rectangular, or other suitable shapes. The hole 20 is positioned so as not to be blocked when the catalyst-activated sheets 10 are stacked.According to one embodiment, the hole 20 is located closer to the base of the flange than to the free end of the flange 18.

[0050] Referring to Figures 18 and 19, a catalytic reactor 22 according to a first embodiment is schematically shown. The catalytic reactor 22 comprises a stack of catalytically active sheets 10. The catalytically active sheets 10 have a central opening 17, and at least some of the catalytically active sheets in the stack have axially extending flanges at least partially positioned around the central opening 17, with the flange 18 of one catalytically active sheet 10 extending into the central opening 17 of an adjacent catalytically active sheet 10. In Figures 18 and 19, the catalytically active sheets 10 are shown as a mesh structure. For example, the catalytically active sheets 10 are arranged as described with reference to Figures 12 to 14. Alternatively, the catalytically active sheets 10 are formed of a plate material having apertures 21 in the radially extending portion 19, and at least some of the catalytically active sheets 10 are formed together with flanges 18 having holes 20, as described with reference to Figures 15 to 17.

[0051] In the illustrated embodiment, the catalytic reactor 22 comprises an optional reaction vessel 23, and the stack of catalytic active sheets 10 is arranged inside the reaction vessel 23. The reaction vessel 23 is provided with an inlet 24 for a first reactant. For example, the first reactant is a fuel such as a gaseous fuel. According to one embodiment, the first reactant is a mixture of fuels. The inlet 24 for the first reactant is provided to guide the first reactant to a central opening 17 of the catalytic active sheet 10. For example, the inlet 24 for the first reactant is aligned with the central opening 17. In the illustrated embodiment, the inlet 24 for the first reactant is provided at a first end of the reaction vessel 23, for example, in the center of the first end. The reaction vessel 23 is provided with one or more inlets 25 for a second reactant. For example, the second reactant is air or oxygen. For example, the reaction vessel 23 includes at least two, at least four, or six or more inlets 25 for a second reactant, located radially outward from the inlet 24 for the first reactant. In the embodiments of Figures 18 and 19, the inlets 25 for the second reactant are located at the first end of the reaction vessel 23, i.e., at the same end as the inlet 24 for the first reactant. The inlets 25 for the second reactant are distributed around the inlet 24 for the first reactant. For example, where applicable, the inlets 25 for the second reactant may be aligned with the aperture 21 of the radially extending portion 19 of the catalytically active sheet 10. The reaction vessel 23 also includes one or more outlets 26 for the product. For example, the product is, for example, a combustion gas containing carbon dioxide. In the illustrated embodiments, the outlets 26 are located radially outward from the stack of catalytically active sheet 10, but they may be located at any suitable location. Either the second end of the reaction vessel 23 is blocked, or at least the end of the stack of catalytically active sheets 10 opposite the first reactant inlet 24 is blocked.

[0052] Referring to Figure 19, the flows of the first and second reactants and products are schematically shown. The first reactant is guided into the central opening 17 of the catalytic sheet 10 in an axial flow indicated by arrow R1. The first reactant is guided axially into the central opening 17 at one end of the stack of the catalytic sheet 10. For example, the first reactant R1 is guided into the reaction vessel 23 through the inlet 24 for the first reactant. Alternatively, the first reactant is guided directly into the central opening 17 at one end of the stack. The first reactant R1 is guided by the flange 18 through the central opening 17 to the closed end on the opposite side of the stack of the catalytic sheet 10, and the first reactant is pushed radially outward through the mesh or holes 20 of the flange 18, etc., and radially pushed in the gaps between the radially extending portions 19 of the catalytic sheet 10, etc. A portion of the flow of the first reactant is further guided axially by the flange 18, and a portion of the flow is pushed radially outward. For example, once a predetermined pressure is achieved inside the reaction vessel 23, the first reactant is pushed radially outward. The radial flow of the first reactant further outward through the flange 18 is indicated by the arrow. At the same time, the second reactant is guided axially through the radially extending portion 19, for example, by the radially extending portion 19 formed of mesh material, or through its aperture 21, and the axial flow of the second reactant is indicated by the arrow R2. For example, the second reactant R2 is guided into the reaction vessel 23 through the inlet 25 for the second reactant. The first reactant is pushed radially and then collides with the axial flow of the second reactant R2, and the first and second reactants react to form a product. The product is then guided out of the reaction vessel 23 through the outlet 26. Thus, the concentration of the first reactant is higher closer to the central opening 17 and flange 18 than further outward in the radial direction, and the concentration of the first reactant decreases radially. At the same time, the concentration of the second reactant is further increased radially in the stack of catalyst-active sheets 10, for example, at the radial level supplied to the stack of catalyst-active sheets 10. For example, the concentration of the second reactant increases radially between the flange 18 and the radial level into which the second reactant is introduced.Naturally, the concentration of the product increases radially outward.

[0053] Referring to Figures 20 and 21, a second embodiment of the catalytic reactor 22 is schematically shown, where the inlet 25 for the second reactant is located at the second end of the reaction vessel 23, opposite the first end and opposite the inlet 24 for the first reactant. The inlet 25 is located radially outward from the central opening 17. Thus, the second reactant is introduced into the stack of the catalytic active sheet 10 in the axial direction opposite to that of the first reactant, indicated by arrow R1 for the first reactant and arrow R2 for the second reactant. The central opening 17 at the opposite end of the stack is closed as the first reactant is introduced, pushing the first reactant radially into contact with the flow of the second reactant R2 and forming the product as described above. Alternatively, the second end of the reaction vessel is closed away from the inlet 25 for the second reactant, pushing the first reactant radially.

[0054] The inlets 25 for the second reactant are described above as a plurality of inlets dispersed around axis A of the stack of the catalytically active sheet 10. Alternatively, the second reactant is guided to a radially extending portion 19 at one end of the stack through an annular orifice or annular inlet extending radially outward from the central opening 17.

[0055] Referring to Figure 22, a portion of the catalytically active product 10 according to another embodiment of the present invention is schematically shown. The catalytically active product 10 of Figure 22 has similar applications to those described above with reference to Figure 1. Furthermore, the catalytically active product 10 of Figure 22 includes a substrate 11, a ceramic material 14, pores 15, and a catalytically active material 16, as described above with reference to Figure 1. However, instead of a layer 12 of the first material and particles 13 of the second material for attaching the ceramic layer 14 to the substrate 11, the embodiment of Figure 22 includes a layer of the first metal 27 formed by the method described with reference to Figures 23 to 27 to form an adhesion layer for fixing the ceramic layer 14 to the substrate 11.

[0056] Referring to Figure 23, a substrate 11 is provided. For example, the substrate 11 is made of a metal or an alloy, or contains a metal or an alloy. According to one embodiment, the substrate 11 is made of steel such as stainless steel. Alternatively, the substrate 11 is made of aluminum or copper. For example, the substrate 11 is formed as a mesh or plate material, for example, in the form of a sheet, as described above.

[0057] The substrate 11 is provided with a thermite or thermite composition 28 shown in Figure 24. The thermite composition is a thermite composition to which materials such as nitrates, graphite, or other materials, or mixtures thereof, are added to facilitate ignition or to impart other desired properties to the composition 28. Therefore, the expression thermite composition includes thermite compositions. The thermite composition 28 comprises at least a first metal oxide and a second metal powder. For example, the second metal powder is an elemental metal. For example, the thermite composition 28 is deposited directly onto the substrate 11. According to one embodiment, the thermite composition 28 is provided as a suspension such as a paste or slurry. For example, the thermite composition 28 is deposited on the surface of the substrate 11 by, for example, spraying at room temperature. Alternatively, the thermite composition 28 is applied onto the substrate 11 by another coating process such as painting or dipping. The oxide of the first metal 27 in the thermite composition 28 is a transition metal oxide such as iron oxide, manganese oxide, chromium oxide, or copper oxide. The second metal in the thermite composition 28 is an alkaline earth metal or transition metal that is more easily oxidized than the first metal 27. For example, the second metal in composition 28 is aluminum. In the schematic diagram, the thermite composition 28 is provided on only one side of the substrate 11. However, it is understood that the thermite composition 28 may be provided on opposing sides of the plate material or on all surfaces of the mesh or any desired surface.

[0058] After the thermite composition 28 is deposited onto the substrate 11, the substrate 11 having the thermite composition 28 is heated to a temperature at which the oxide of the first metal is reduced to the first metal 27 in an exothermic reaction, and the second metal is oxidized to the oxide of the second metal 29, which is schematically shown in Figure 25. During this reaction, heat is generated, and as a result, the first metal 27 is bonded to the substrate 11 by welding or partially melting the surface of the first metal and / or the substrate 11.

[0059] After cooling, the substrate 11 having oxides of the first metal 27 and the second metal 29 is cleaned to remove the oxide of the second metal 29 and, if applicable, other residues, thereby achieving a porous layer of the first metal 27 with a rough surface, which is schematically shown in Figure 26. For example, the cleaning process is carried out by cleaning with water or other suitable liquid.

[0060] Next, a ceramic layer 14 having pores 15 is provided on the substrate 11 having a layer of the first metal 27, as shown in Figure 27 and described in more detail above. Thus, the ceramic layer 14 is deposited on the rough surface of the porous layer of the first metal 27 by spraying, followed by drying and firing, and the ceramic layer 14 is reliably bonded to the substrate 11 via the layer of the first metal 27. Optionally, the ceramic layer 14 may contain a pore-forming agent provided to form more pores 15 in the ceramic material 14. Next, the catalytically active material 16 is provided to the ceramic layer 14, for example, by impregnation, dipping, or spraying. The catalytically active material 16 can be deposited on the surface of the ceramic layer 14 and within its pores 15 by a conventional impregnation process. After the deposition of the catalytically active material 16, a heating process is carried out to form the final catalytically active product 10.

Claims

1. A method for producing catalytically active products, a) The step of providing a substrate (11), b) A step of depositing a thermite or thermite composition (28) on the substrate (11), wherein the composition (28) comprises at least an oxide of a first metal (27) and powder of a second metal (29), c) Heating the substrate (11) having the composition (28) to a temperature at which the oxide of the first metal (27) is reduced to the first metal (27) in an exothermic reaction, thereby oxidizing the second metal (29) to an oxide of the second metal (29), and thereby bonding the first metal (27) to the substrate (11) by the heat from the reaction, d) A step of washing the substrate (11) having oxides of the first metal (27) and the second metal (29) with water to remove the oxide of the second metal (29), thereby forming a porous layer of the first metal (27) on the substrate (11), wherein the layer has a rough surface, e) A step of depositing a ceramic material on the rough surface of the first metal (27) to form a ceramic layer (14) thereon, f) The step of adding the catalytic active material (16) to the ceramic layer (14), Includes, A method wherein the oxide of the first metal (27) in the composition (28) is a transition metal oxide, and the second metal (29) in the composition (28) is an alkaline earth metal or transition metal that is more easily oxidized than the first metal (27).

2. The method according to claim 1, further comprising the step of providing the thermite or thermate composition (28) in the form of a suspension and spraying it onto the substrate (11) in step b).

3. The method according to claim 2, wherein the thermite or thermate composition (28) is sprayed onto the substrate (11) at room temperature.

4. The method according to any one of claims 1 to 3, further comprising the step of providing the ceramic material as a suspension, and spraying the ceramic material onto the layer of the first metal (27) to form the ceramic layer (14).

5. The method according to claim 4, wherein the ceramic material is sprayed at room temperature.

6. The method according to any one of claims 1 to 3, further comprising the step of adding the catalytically active material (16) to the ceramic layer (14) by impregnation, immersion, or spraying in step f).

7. The method according to any one of claims 1 to 3, wherein the substrate (11) is made of a metal or an alloy.

8. The method according to any one of claims 1 to 3, wherein the second metal (29) in the composition (28) is aluminum.

9. The ceramic layer (14) is made of Al ２ O ３ SiO ２ , TiO ２ , ZrO ２ , CEO ２ The method according to any one of claims 1 to 3, or a mixture thereof.

10. The method according to any one of claims 1 to 3, wherein the catalytic active material (16) comprises a noble metal, a transition metal, an oxide thereof, or a mixture thereof.

11. A catalytically active product comprising a substrate (11), a layer of metal (27) bonded to the substrate (11), and a ceramic layer (14) bonded to the metal (27), wherein pores (15) containing a catalytically active material (16) are formed in the ceramic layer (14).

12. The catalytically active product according to claim 11, wherein the substrate (11) includes a metal (27), and the layer of the metal (27) is formed of a transition metal.

13. The catalytically active product according to claim 11, wherein the catalytically active material (16) comprises a noble metal, a transition metal, or a mixture or oxide thereof.

14. The ceramic layer (14) is Al ２ O ３ , SiO ２ , TiO ２ , ZrO ２ , CeO ２ or a mixture thereof, the catalytically active product according to claim 11.

15. A catalytic reactor (22) comprising a central axis (A) and a stack of catalytically active sheets (10), wherein the catalytically active sheets (10) are stacked in the axial direction, and each of the catalytically active sheets (10) is formed of the catalytically active product described in claim 11.

16. The catalytic reactor (22) according to claim 15, wherein each of the catalytic active sheets (10) has a central opening (17), and at least some of the catalytic active sheets (10) have axially extending flanges (18) at least partially disposed around the central opening (17), and the axially extending flange (18) of one of the catalytic active sheets (10) extends into the central opening (17) of an adjacent catalytic active sheet (10).

17. The catalytic reactor (22) according to claim 16, wherein each of the catalyst-activated sheets (10) includes a radially extending portion (19) that extends radially from the central opening (17).

18. The catalytic reactor (22) according to claim 17, wherein the radially extending portion (19) of one catalytically active sheet (10) is arranged with a gap between it and the radially extending portion (19) of an adjacent catalytically active sheet (10).

19. The catalytic reactor (22) according to claim 16, wherein the axially extending flange (18) is provided with a through hole (20).

20. The catalytic reactor (22) according to claim 17, wherein the radially extending portion (19) is provided with through-apertures (21) distributed around the central opening (17).

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