Patent Grant
11660582
This patent application is a 371 of International Application No. PCT/EP2018/052238, filed Jan. 30, 2018 which claims the priority of European Application No. 17154045.3, filed Jan. 31, 2017, each of which are incorporated herein by reference in their entirety.
The present invention relates to a method of producing a pellet, to a pellet, to a catalyst charge, and to a static mixer having a plurality of pellets.
Methods of producing ceramic pellets are generally known. A strand is, for example, first produced by means of extrusion and is subsequently cut up to obtain individual pellets. Such pellets can be used as catalysts. Monolithic catalysts are also known that comprise ceramics, metal foam, networks, or so-called honeycomb structures.
Metal foam can be produced, for example, as described in WO 2016/020053 A1. In this respect, a polyurethane foam is first galvanized with a metal. The polyurethane foam is subsequently removed by pyrolysis so that a metal foam material is obtained. This metal foam material can finally be converted into a metal foam by a subsequent sintering. Prior to the sintering a metal powder can also be applied to the metal foam material that can then, for example, form an alloy in the form of a metal foam on the sintering with the metal foam material.
A catalyst charge has a decisive influence on the fluid dynamics in a reactor and thus on the heat transfer and mass transfer and on the pressure loss. A denser catalyst bed thus, for example, leads to an increased pressure loss. At the same time, the mass transfer can be particularly good in a denser catalyst bed since the densely packed catalyst charge generates a great deal of turbulence, which is accompanied by an improved convective heat transfer.
The heat transfer is a decisive parameter that has to be optimized both for endothermic and for exothermic reactions and that significantly influences the heat supply and removal property of a reactor. The heat transfer is limited in dependence on the temperature range in a chemical reactor by conduction, convection, or radiation. There is a tendency to the effect that the contribution of the heat transfer by radiation increases as the temperature increases. Examples for methods that are limited by the heat transfer due to radiation are methods that are based on extremely endothermic reactions such as steam reforming. The challenge in these methods is to introduce sufficient thermal energy into the reactor to instigate the chemical reactions. Typical reaction temperatures are above 900° C. At temperatures of less than 800° C. the heat transfer is typically limited by convection. The convection is highly dependent on fluid dynamics and is promoted in turbulent flows. A typical parameter for the turbulence in a reactor is the Reynolds number.
To participate in chemical reactions in a porous material, it is necessary that a fluid moves to catalytically active centers of the porous material. The mass transfer to such catalytically active centers in porous materials is mainly determined by how large the portion of the fluid is that penetrates into the porous material or by how much of this fluid flows past the porous material without penetrating into the pores.
One of the most important parameters for the costs of a chemical process is the pressure loss. The higher the pressure loss is, the higher the required effort to convey a fluid through a reactor. The operating costs of a reactor thus also increase as its pressure loss increases. However, a certain pressure loss is indispensable to generate desired turbulent flows in a reactor.
It is understood that the above considerations on fluid dynamics also apply accordingly to static mixers such as in absorption columns or distillation columns.
It is the underlying object of the invention to provide a method in accordance with which pellets can be produced by which the fluid dynamics in reactors or columns can be optimized and set in a targeted manner so that the heat transfer and mass transfer as well as the pressure loss in a reactor or in a column can hereby be optimized.
A method having the features of claim 1 is provided to satisfy the object.
The method in accordance with the invention of producing a pellet, in particular for a catalyst and/or for a static mixer, comprises a cutting to shape and/or shaping of at least one layer of metal foam material into a pellet form.
The method in accordance with the invention permits an economical and controlled production of pellets having different shapes. The design freedom with respect to the geometry and size of the pellets provided by the method permits different packings of catalyst beds and/or of static mixers with adapted fluid dynamics so that the heat transfer and mass transfer as well as the pressure loss in a reactor can be optimized.
Advantageous embodiments of the invention can be seen from the dependent claims, from the description and from the drawing.
In accordance with an embodiment, the metal foam material is sintered, for example to convert a metal foam material comprising different metals into a metal alloy foam. The sintering can, for example, take place at a temperature of 500° C. to 1200° C. in an oxidative or reductive atmosphere. Different alloys can hereby be obtained that can have optimized properties for the planned purpose of use of the pellets.
The stability of the pellets is additionally increased by the sintering, whereby pellet shapes can be implemented that are not possible with pellets composed of ceramic materials. The high stability of the pellets additionally permits a very fast and efficient packing of the catalyst bed; in addition, higher packing densities can be achieved. The same applies accordingly to static mixers set up from individual pellets.
In accordance with a variant of the method, the shaping into pellets is carried out by the cutting to shape and/or shaping prior to sintering. Alternatively, however, it is equally possible to carry out the step of cutting to shape and/or shaping only after sintering. The optimum order of the steps ultimately depends on the desired pellet shape.
The metal foam is preferably an open-pore metal foam. It is hereby possible for fluids such as gaseous reactants to penetrate through the total pellet and to participate in reactions within the pellet. In accordance with a preferred embodiment, the metal foam comprises a catalytically active material that can catalyze heterogeneous reactions and is in particular suitable for converting gaseous reactants.
The metal foam preferably comprises at least one of the elements Ni, Fe, Cr, Al, Nb, Ta, Ti, Mo, Co, B, Zr, Mn, Si, La, W, Cu, Ag, Au, Pd, Pt, Zn, Sn, Bi, Ce, and/or Mg. The metal foam particularly preferably comprises at least one of the elements Ni, Fe, Cr and/or Al and very particularly preferably at least one of the elements Ni and/or Al. A plurality of these elements can together form a component of the metal foam as an alloy or can be present as particles on the metal foam.
The metal foam preferably has pores having diameters that are distributed in a monomodal or multimodal manner, in particular in a bimodal manner. In accordance with a particularly preferred embodiment, the pores are distributed in a multimodal manner and are spatially arranged within the pellet such that pores are present in a first region of the pellet having larger diameters than in a second region of the pellet spatially separate therefrom. Pores having different diameters can be used to influence the dwell time of reactants and products within a pellet. The formation of turbulence can also be influenced by pores that differ with respect to their sizes, types, or geometries, whereby the heat transfer and mass transfer can be influenced.
In accordance with a particularly preferred further development of the method in accordance with the invention, at least two layers of different metal foam material are provided. Layers of metal foam materials are inter alia also considered as different that differ with respect to the orientation of the pores contained therein, that comprise different materials, that differ with respect to their thicknesses and/or that have different gas permeabilities. It is in particular preferred that the at least two different layers differ with respect to their porosities, their pore diameters, their material compositions and/or their gas permeabilities. The fluid dynamic properties of the pellet can be set in a targeted manner by the use of different layers and thus of the heat transfer and mass transfer as well as the pressure loss in a reactor that has a catalyst having a plurality of such pellets or in an absorption column or distillation column having a static mixer composed of a plurality of such pellets.
The two layers of metal foam material can, for example, be connected to one another by pressing and/or by soldering by means of a soldering film. A pressing permits to layers to be connected without using an additional material that could possibly be disruptive on a use of the resulting pellet as a catalyst charge and/or as a static mixer. The user of a soldering film makes it possible to insert a solder compound into the pellets in a targeted manner, by which compound, for example, the fluid dynamics within the pellet can be controlled.
For example, the cutting to shape and/or shaping of the at least one layer of the metal foam material takes place by means of laser cutting, waterjet cutting, spark erosion, machining, in particular sawing, drilling, turning, or grinding, controlled crushing, twisting, rolling, pressing, folding, heat treatment, in particular welding with an arc, separation welding, or treatment with a soldering lamp, chemical treatment, in particular leaching or separation.
The pellet preferably has a volume of 0.5 mm3 to 30 cm3, particularly preferably of 0.8 mm3 to 15 cm3, and very particularly preferably from 2 cm3 to 10 cm3. With a pellet having a volume of less than 0.5 mm3 there is a risk that they are carried out of the reactor by the reactant flow, in particular on a use as a catalyst for heterogeneous reactions. A pellet having a volume of less than 0.5 mm3 additionally only generates a little turbulence in a reactor and thus contributes little to the convective heat transfer and mass transfer. Catalyst charging processes using pellets that have a volume of more than 30 cm3 in contrast form empty spaces that are disadvantageous for the convective heat supply and removal and in particular contribute to unwanted hot spots and to a reduction of the process stability in highly exothermic reactions. On the other hand, empty spaces can promote the heat supply and removal by radiation at temperatures of more than 800° C. The heat supply and removal can accordingly be optimized for all process conditions by the targeted influencing of the size or number of the empty spaces.
The metal foam material preferably has pores that have diameters of 10 μm to 10,000 μm, preferably of 50 μm to 3000 μm, very particularly preferably of 100 μm to 1500 μm. Pores having diameters of less than 10 μm result in a deterioration of the mass transfer properties. Better heat transfer properties and mass transfer properties can be achieved using metal foam material that has a pore diameter of 10 μm or more. However, with pores having a diameter of more than 10,000 μm the efficiency of a reactor having such pellets as the catalyst charge is reduced due to a reduced ratio of a catalytically active surface provided by the metal foam to the inner volume of the pores.
The porosity of the pellet is preferably greater than or equal to 70%, particularly preferably greater than or equal to 80%, and very particularly preferably greater than or equal to 85%. They are consequently pellets of highly porous material. The porosity here designates the quotient from the volume of the pores in a pellet to the total volume of the pellet. It has been found that a porosity of less than 70% has a negative effect on the mass transfer and on the pressure loss when such a pellet is used in a catalyst bed. The porosity is here determined by means of an image analysis with reference to a transverse cross-section of the pellet. A transverse cross-section of the pellet is prepared for this purpose and an image is taken of it. To determine the porosity, the image surfaces with and without material, i.e. the material regions and the hole regions, are put into relationship with one another. A porosity of 50%, for example, means that the surfaces with and without material are of equal size in the taken image. The higher the proportion of the surface without material in the taken image, the higher the porosity of the pellet.
It is understood that due to a suitable form of the pellet, a static mixer set up therefrom can also be ideally adapted to its respective application, for example in an absorption column or in a distillation column.
A further subject matter of the invention is a pellet that comprises at least one layer of metal foam and can in particular be obtained in accordance with one of the above-described methods. The pellet can, for example, be provided for a catalyst charge and/or for a static mixer, for example for an absorption column or distillation column.
The metal foam is preferably an open-pore metal foam. It is hereby possible for gaseous reactants to penetrate through the total pellet and to participate in reactions within the pellet. In accordance with a preferred embodiment, the metal foam comprises a catalytically active material that can catalyze heterogeneous reactions and is in particular suitable for converting gaseous reactants.
In accordance with a first variant, the pellet comprises at least one outer-side indentation, one outer-side groove and/or at least one winding and/or twist of a layer of metal foam. The fluid dynamics can be influenced in a manner suitable for the respective application by this shape and the heat transfer properties and the mass transfer properties of a reactor or of a column can be optimized.
A second variant of the pellet provides that at least one outer surface and/or one inner boundary surface of the pellet is at least partly closed. A closed outer surface is understood as an outer surface of a pellet that does not have any pore openings so that gaseous reactants cannot enter into the pellet or escape from the pellet through them. A closed inner boundary surface of a pellet accordingly designates a surface in the interior of the pellet that is not penetrated by pores. Such an inner boundary surface can, for example, exist between two layers of metal foam that are connected to one another while using a soldering film. Such partly closed outer surfaces and/or inner boundary surfaces can contribute to turbulence in a gas flow flowing through the reactor or the column and can influence the fluid dynamics, whereby ultimately the heat transfer properties and mass transfer properties of a reactor or of a column can be optimized.
In accordance with a third variant, the pellet comprises at least two different layers of metal foam. Different properties can be combined in a pellet using different layers of metal foam, whereby the fluid dynamics and thus the heat transfer properties and mass transfer properties and the pressure loss of a reactor or of a column can in turn be optimized.
The first, second, and third variants do not preclude one another, but can rather also be present in combination so that in one variant the pellet comprises at least one outer-side indentation, an outer-side groove and/or at least one winding and/or twist of a layer of metal foam and at least one outer surface and/or one inner boundary surface of the pellet is at least partly closed. In accordance with a further variant, the pellet comprises at least one outer-side indentation, an outer-side groove and/or at least one winding and/or twist of a layer of metal foam and at least two different layers of metal foam, with at least one outer surface and/or one inner boundary surface of the pellet being at least partly closed. Provision is made in accordance with a further alternative that the pellet comprises at least one outer-side indentation, an outer-side groove and/or at least one winding and/or twist of a layer of metal foam and at least two different layers of metal foam. Finally, the pellet can comprise at least two different layers of metal foam and at least one outer surface and/or one inner boundary surface of the pellet can be at least partly closed.
The pellet preferably comprises a metal foam preferably comprising at least one of the elements Ni, Fe, Cr, Al, Nb, Ta, Ti, Mo, Co, B, Zr, Mn, Si, La, W, Cu, Ag, Au, Pd, Pt, Zn, Sn, Bi, Ce, and/or Mg. The metal foam particularly preferably comprises at least one of the elements Ni, Fe, Cr and/or Al and very particularly preferably at least one of the elements Ni and/or Al. A plurality of these elements can form an alloy and can make up a component of the metal foam or the total metal foam. In addition, these elements can be included in particles that are present within the metal foam. The metal foam particularly preferably comprises a nickel-iron-chromium-aluminum alloy and/or a nickel-chromium-aluminum alloy. The nickel-iron-chromium aluminum alloy and/or the nickel chromium aluminum alloy can be doped with further elements to set and optimize the catalytic activity.
Very particularly preferably the metal foam at least substantially comprises a nickel-iron-chromium-aluminum ally and/or a nickel-chromium-aluminum alloy. This means that, except for a possibly doped nickel-iron-chromium-aluminum alloy and/or a nickel-chromium-aluminum alloy, the metal foam only includes unavoidable contaminants and/or residues of a soldering film possibly used in the production.
In accordance with an embodiment, the metal foam has pores having diameters that are distributed in a monomodal or multimodal manner, in particular a bimodal manner.
The pores in the pellet preferably have diameters of 10 μm to 10,000 μm, preferably of 50 μm to 3000 mm, very particularly preferably of 100 μm to 1500 μm. Pores having diameters of less than 10 μm can lead to an increased pressure loss and can impede the heat transfer and mass transfer. Considerably better heat transfer properties and mass transfer properties as well as a reduced pressure loss can be achieved using pellets that have pore diameters above 100 μm. However, with pores having a diameter of more than 10,000 μm the efficiency of a reactor having such pellets as the catalyst charge is reduced due to a reduced ratio of a catalytically active surface provided by the metal foam to the inner volume of the pores.
The present invention also relates to a catalyst charge having a plurality of pellets in accordance with at least one of the above-described aspects.
The catalyst charge in accordance with the invention can, for example, be used in a heterogeneously catalyzed reaction. The reactants and products of the heterogeneously catalyzed reaction can be present in gaseous and/or liquid form here. The catalyst charge in accordance with the invention can furthermore be used in the conversion of natural gas in longer chain hydrocarbons, in the hydrogenation/dehydrogenation of hydrocarbons, in particular in steam reformation, in oxidation reactions, in particular in partial ethylene oxidation.
Yet a further subject matter of the invention is a static mixer, for example for an absorption column or for a distillation column, having a plurality of pellets of the above-described kind.
In accordance with an embodiment, the plurality of pellets of the catalyst charge or of the static mixer comprise different pellets, in particular pellets that differ with respect to their sizes, shapes, surfaces, densities, porosities and/or their materials. It is hereby possible to influence the fluid dynamics and thus the heat transfer and mass transfer in a suitable manner and thus to optimize the heat supply and removal properties of the reactor.
In accordance with a further embodiment, the different pellets are uniformly distributed in the catalyst charge or in the static mixer. In accordance with another embodiment, the distribution of the different pellets has a gradient in an axial direction and/or a gradient in a radial direction. The axial direction designates the direction from a reactor inlet or a column inlet to a reactor outlet or a column outlet and the radial direction designates the direction transverse to the axial direction. In accordance with yet a further embodiment, the distribution of the different pellets has discrete layers in the axial direction and/or in the radial direction. A variation of the composition of the catalyst charge or of the static mixer in the radial direction makes it possible to influence the heat supply and removal properties in a targeted manner up to and into the interior of the reactor or of the column and thus to correspondingly optimize the reactor or the column. A change of the composition of the catalyst charge or of the static mixer in the axial direction enables an adaptation of the fluid dynamics to a composition of the reactor flow changing in the axial direction.
The invention will be described in the following purely by way of example with reference to possible embodiments and to the enclosed drawing. There are shown:
To form pellet-like metal foam blanks 16 from the metal foam material 14, different techniques can be made use of, for example, laser cutting, waterjet cutting, spark erosion, machining, in particular sawing, drilling, turning, or grinding, controlled crushing, twisting, winding, rolling, pressing, folding, heat treatment, in particular welding with an arc, separation welding, or treatment with a soldering lamp, chemical treatment, in particular leaching or separation.
It can also be advantageous in the production of pellet-like metal foam blanks 16 having a helical shape such as shown in the middle of
In accordance with an alternative embodiment, it is moreover conceivable to carry out the method step S4 before the method steps S2 and S3. With this alternative, the layer 12 of metal foam material 14 is therefore first sintered and subsequently comminuted as described above and shaped to finished pellets 10.
The pellet 10 shown in
The pellet 10 shown in
Seven indentations 40 are represented in the multilayer pellet 10 shown in
All the pellets 10 shown in
It is also possible to first roll up one or more layers 12 of the metal foam material 14, as shown at the left in
The helical pellet 10 is very compact, which has an advantageous effect on the heat transfer properties and mass transfer properties. The mass transfer properties of such helical pellets 10 are in particular improved due to the short transfer distances. An axial passage that can reduce the pressure loss of a corresponding catalyst bed is produced in the inner region of the pellet 10 by the rolling up. A statistical packing of a catalyst bed with helical pellets 10 produces particularly strong turbulence. However, an ordered packing can also be implemented in addition to a statistical packing by the helical pellets 10. The helical pellets 10 can thus be stacked to improve the heat transfer and mass transfer in the catalyst bed to generate channels in a targeted manner in the catalyst bed to hereby configure flow profiles in the catalyst bed.
Spiral pellets 10 can also be produced by twisting or winding strip-like metal foam material 14. The pellet 10 shown in
Pellets 10 having the shapes shown in
Different layers 12 of metal foam of a pellet 10 can also be twisted or wound in opposite directions to produce a pellet 10 as shown in
Pellets 10 having the shapes shown in
The pellets 10 of
Very densely packed catalyst beds can be obtained and flow profiles can be produced in a targeted manner in the catalyst bed by a vertical packing of the pellets 10 shown in
The pellet 10 shown in
Schematic cross-sections of pellets 10 having three or two different layers 12 are shown in
The diameter of the first pores 52 can be in the range of 500 μm to 10,000 μm and the diameter of the second pores 54 can be in the range of 10 μm to 3000 μm. Such a distribution of the pores 52, 54 can be used, for example, to influence the dwell time of reactants in the pellet 10. The smaller pores 54 in the interior of the pellet shown in
The pellet 10 shown in
A closed outer surface 56 can, for example, be produced by applying a soldering film 30 to an outer surface 32 of a pellet 10 and by a subsequent heating of the soldering film 30. It is also possible to produce inner boundary surfaces in a pellet 10, that can be partly or completely closed, in a metal foam material 14 having a plurality of layers 12 that are connected by means of soldering films 30. Partly or completely closed inner boundary surfaces likewise influence a reactant flow 36 that has penetrated into the pellet. The dwell time of the reactants within the pellet 10 can, for example, hereby be varied or turbulence can be produced in the reactant flow 36.
A reactor 22 flowed through by a reactant flow 36 is shown in a perspective view in
It is also conceivable that the catalyst filling 20 gradually changes along the axial direction L of the reactor 22. This means that a first kind or mixture of pellets 10 is provided in the region of a reactor inlet 64 in which the reactant flow 36 enters into the reactor 22 and a second kind or mixture of pellets 10 is provided in a region of the reactor outlet 66. The first kind or mixture of pellets 10 merges along the axial direction L of the reactor into the second kind or mixture of pellets 10. A different fluid-dynamic environment can hereby be provided at the reactor inlet 64 than at the reactor outlet 66.
The distribution of different pellets 10 in the catalyst charge can take place homogeneously, gradually, or in discrete rings in the radial direction R. It can be recognized in the cross-sectional view of a reactor shown in
A partly transparent view of a reactor is shown in
A comparison of pellets 10 composed of metal foam 24 with conventional ceramic pellets is shown in Tables 1 and 2 and in
Five examples for pellets 10 in accordance with the invention are listed in Table 1 with a cube or disk geometry that each comprise a nickel-chromium-aluminum alloy (NiCrAl) and two comparison examples of ceramic pellets that comprise calcium aluminate.
1 Cube with six layers, compressed by 20%
2 Dimensions relate to length × width × thickness
3 Cylinder with notches, a maximum outer diameter of 13 mm, a length of 17 mm, and four identical cylindrical hollow spaces having arched ends and an inner diameter of 3.5 mm in each case
4 Hollow cylinder with an outer diameter of 8 mm, a length of 8 mm, and an inner diameter of 3.0 mm
It can be recognized with reference to Examples 1 to 5 that pellets 10 can be produced by the method in accordance with the invention with different effects on the pressure loss, i.e. the pellets 10 can be easily adapted to the demands of their planned area of use. For example, a change of the pore diameters can be used to influence the pressure loss, as is shown with reference to Examples 1 and 2. The use of a pellet 10 having a plurality of layers 12 reduces the pressure loss and simultaneously improves the mass transfer properties, as can be recognized with reference to Examples 3 and 4. Both the pressure loss and the mass transfer can be optimized in dependence on the purpose of use of the pellets 10 by a change of the shape of the pellets 10. The disk-shaped pellet 10 in accordance with Example 5 has equally good mass transfer properties as a pellet in accordance with Example 3, but with an increased pressure loss.
The lower curve marked by diamonds in
Mean heat transfer coefficients that are shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 17154045 | Jan 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/052238 | 1/30/2018 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/141729 | 8/9/2018 | WO | A |
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| Number | Date | Country | |
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| 20190388867 A1 | Dec 2019 | US |
