Process for producing a catalyst and catalyst as such

Abstract

To be able to produce an SCR catalyst (2), in particular one having a zeolite fraction (Z) as catalytically active fraction, in a reliable process and at the same time achieve good catalytic activity of the catalyst (2), an inorganic binder fraction (B) which is catalytically inactive in the starting state and has been treated to develop catalytic activity is mixed into a catalyst composition (4). The inorganic binder component for the binder fraction (B) is, in the starting state, preferably porous particles (10), in particular diatomaceous earth, which display mesoporosity. To effect catalytic activation, the individual particles (10) are either coated with a catalytically active layer (12) or transformed into a catalytically active zeolite (14) with maintenance of the mesoporosity.

Claims

1. A process for producing an extruded catalyst, the process comprising extruding a catalyst composition to produce the extruded catalyst body, wherein the catalyst composition comprises an inorganic binder fraction comprising silicate-based particles, at least a portion of which silicate-based particles comprise: (a) particles of diatomaceous earth each coated with a layer of a catalytically active zeolite; (b) particles of diatomaceous earth comprising an internal catalytically active zeolite structure; or (c) both (a) and (b); such that the silicate-based particles exhibit rheological properties suitable for extrusion.

2. The process according to claim 1, wherein the extruded catalyst composition further comprises a catalytically active component admixed with the inorganic binder fraction.

3. The process according to claim 2, wherein the catalytically active component comprises a molecular sieve-based catalyst, a titanium-vanadium-based catalyst, or a tungsten oxide-cerium oxide-based catalyst.

4. The process according to claim 3, wherein the titanium-vanadium-based catalyst is a titanium-vanadium system, a titanium-vanadium-tungsten system, a titanium-vanadium-tungsten silicon system, a titanium-vanadium-silicon system, a titanium-vanadium-tungsten-iron system, a titanium-vanadium-tungsten-silicon-iron system or a titanium-vanadium-silicon-iron system.

5. The process according to claim 3, wherein the tungsten oxide-cerium oxide-based catalyst is a FeW/CeO.sub.2 system or a FeW/CeZrO.sub.2 system.

6. The process according to claim 2, wherein the catalytically active component comprises a crystalline aluminosilicate zeolite.

7. The process according to claim 6, wherein the crystalline aluminosilicate zeolite has the framework structure CHA, AEI, ERI, MFI, BEA, FAU, AFX or FER.

8. The process according to claim 6, wherein the crystalline aluminosilicate zeolite is activated with copper or iron.

9. The process according to claim 1, wherein the diatomaceous earth particles have a mesoporosity or macroporosity with pores having diameters greater than 2 nm.

10. The process according to claim 9, wherein the particles of diatomaceous earth have pores with diameters greater than 5 nm.

11. The process according to claim 1, wherein the particles of the inorganic binder fraction comprises particles of diatomaceous earth, each coated with the layer of catalytically active zeolite.

12. The process according to claim 11, wherein the layer of catalytically active zeolite has a thickness that is less than 20% of the average particle diameter of the particles of diatomaceous earth.

13. The process of claim 11, wherein the particles of diatomaceous earth, each coated with the layer of catalytically active zeolite, are prepared by coating particles of diatomaceous earth with catalytically active zeolite particles.

14. The process of claim 11, wherein the particles of diatomaceous earth, each coated with the layer of catalytically active zeolite, are prepared by coating particles of diatomaceous earth with catalytically inactive zeolite particles to form a coated composition and subjecting the coated composition to an exchange with one or more ions of a catalytically active metal.

15. The process according to claim 1, wherein the inorganic binder comprises particles of diatomaceous earth comprising an internal catalytically active zeolite structure.

16. The method of claim 15, wherein the particles of diatomaceous earth that have been transformed to contain an internal catalytically active zeolite structure are prepared by: (a) hydrothermally treating particles of diatomaceous earth under conditions sufficient to crystallize at least a portion of the internal structure of the particles of the diatomaceous earth to form hydrothermally treated particles containing a zeolite structure and having a morphology of the diatomaceous earth particles; (b) calcining the hydrothermally treated particles to form calcined particles having a morphology of the diatomaceous earth particles; and (c) subjecting the calcined particles to an exchange with one or more ions of a catalytically active metal.

17. The method of claim 16, wherein the one or more ions of a catalytically active metal comprise copper or iron ions.

18. The process according to claim 1, wherein the particles of diatomaceous earth have an average particle diameter in the range of from 1 micron to 100 microns.

19. The process according to claim 18, wherein catalytically active layer thickness is in the range of from 0.5 micron to 10 microns.

20. A catalyst produced by a process according to claim 1.

Description

(1) Embodiments of the invention are illustrated below with the aid of the figures. In the figures

(2) FIG. 1 shows a simplified schematic diagram to illustrate the production process,

(3) FIG. 2 shows a schematic diagram to explain the production of particles for the binder component, in which the particles are provided with a catalytically active layer,

(4) FIG. 3 shows a schematic diagram to illustrate the production of particles of the binder component, in which the particles are transformed into a zeolite, and

(5) FIG. 4 shows a schematic diagram to explain the catalytic activation of a pillared clay mineral which is inactive in the starting state as binder component by incorporation of catalytically active cells.

(6) According to FIG. 1, an extrusion process is provided for producing a catalyst 2. A catalyst composition 4 comprising, as main component, a catalytically active zeolite fraction having a zeolite Z as catalytically active component, an inorganic binder fraction B and in addition usually a certain proportion of organic binders O or possibly further additives is initially provided. The zeolite fraction and the inorganic binder fraction B are homogeneously mixed as starting powder together with the organic binder fraction O and optionally further components to give the extrudable catalyst composition 4. The rheological property of the catalyst composition 4 for the subsequent extrusion is appropriately set via the binder fractions B, O, so that the catalyst composition 4 has a plasticizability suitable for the extrusion tool.

(7) A catalyst body 6 is subsequently produced as all-active extrudate by extrusion of this catalyst composition 4 and this catalyst body 6 is firstly dried and subsequently sintered in a furnace 8, so that at the end the ceramic catalyst 2 has been formed as extruded all-active catalyst. In the example, this is a honeycomb catalyst having, for example, a cylindrical basic geometry. The zeolite fraction preferably consists of an iron- or copper-exchanged zeolite Z, in particular of the ZSM-5, beta or chabazite type. The zeolite fraction can also consist of a mixture of such zeolites Z.

(8) The binder fraction B is preferably a powder which is catalytically inactive in the original state and consists of individual particles 10, in particular of a diatomaceous earth. These particles 10 are catalytically activated by means of a pre-treatment during which they maintain their morphology. The particles 10 are preferably porous particles. The particles 10 overall have a mesoporosity having a pore width p (average pore diameter) which is typically >5 nm. A diatomaceous earth, in particular, is employed as starting material for these particles 10. The particles 10 usually have an (average) particle diameter d in the range from a few ?m to some 10 ?m.

(9) In a first embodiment shown in FIG. 2, the particles 10 are coated with a catalytically active layer 12 and catalytically activated in this way. The layer 12 is, in particular, a zeolite layer.

(10) In a second alternative, as shown in FIG. 3, the particles 10 are transformed into zeolitic particles 14 by means of a suitable treatment known per se with maintenance of their general morphology, i.e., in particular, with maintenance of their mesoporosity. Here, the microstructure of the particles 10 is transformed into the tetrahedral structure consisting of silicon oxide/aluminium oxide tetrahedra which is typical of zeolites. At the same time, the mesostructure or macrostructure of the particles 10 with their mesoporosity is maintained.

(11) In the third embodiment as per FIG. 4, pillared clay minerals (pillared clays) are used for the binder fraction B. These pillared clay minerals consist of clay layers 18 kept at a spacing from one another by pillars 16. Catalytically active sites 20 are intercalated into the free spaces between the clay layers 18 in these catalytically inactive structures.

(12) The particles 10 are thus treated and thus catalytically activated before addition to and mixing into the catalyst composition 4. Preference is given to the total binder fraction B, i.e. the entire inorganic starting powder being catalytically treated in this way. As an alternative, only part is treated. It is also possible to employ mixtures of different inorganic binder components, as are shown by way of example in FIGS. 2 to 4, both catalytically inactive and catalytically activated. It is also possible to mix different starting materials, for example different clay minerals, with one another. The binder components are at least largely homogeneously distributed in the finished catalyst 2.

(13) The finished catalyst 2 preferably has a composition consisting of from 50 to 80% by weight of the catalytically active zeolite and from 20 to 50% by weight of the inorganic binder fraction B, in each case based on the total mass of the sintered catalyst 2 in the final state. Further components such as further additives, etc., can also be present. The total proportion of these is not more than 5% by weight. The proportion of the volatile organic binder fractions O is typically a few percent by weight in relation thereto.

LIST OF REFERENCE NUMERALS

(14) 2 Catalyst

(15) 4 Catalyst composition

(16) 6 Catalyst body

(17) 8 Furnace

(18) 10 Particle

(19) 12 Layer

(20) 14 Zeolitic particles

(21) 16 Pillar

(22) 18 Clay layer

(23) 20 Site

(24) Z Zeolite

(25) B Inorganic binder fraction

(26) O Organic binder fraction