EP2361154A1 - Metal-containing crystalline silicates - Google Patents

Metal-containing crystalline silicates

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Publication number
EP2361154A1
EP2361154A1 EP09752302A EP09752302A EP2361154A1 EP 2361154 A1 EP2361154 A1 EP 2361154A1 EP 09752302 A EP09752302 A EP 09752302A EP 09752302 A EP09752302 A EP 09752302A EP 2361154 A1 EP2361154 A1 EP 2361154A1
Authority
EP
European Patent Office
Prior art keywords
silicate
metal
boron
titanium
gallo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09752302A
Other languages
German (de)
French (fr)
Inventor
Klaus Wanninger
Arno Tissler
Anna Omegna
Andreas Pritzl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie IP GmbH and Co KG
Original Assignee
Sued Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Publication of EP2361154A1 publication Critical patent/EP2361154A1/en
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/082—Gallosilicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/30—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead

Definitions

  • the invention relates to novel metal-containing silicates, in particular redox-active and crystalline silicates, a process for the preparation of metal-containing crystalline silicates and their use as high-temperature oxidation catalyst or
  • the invention further relates to a catalytic composition and a
  • Catalyst shaped body containing the metal-containing crystalline silicates Catalyst shaped body containing the metal-containing crystalline silicates.
  • noble metal-containing oxidation catalysts for emission control in both stationary and in mobile applications are known.
  • oxides or oxide mixtures selected from Al, Ti, Ce, La, Zr, Sn, W, Y, Pr, Gd oxides and optionally further alkaline earth oxides are used as active carrier substance. These oxides usually become washcoat
  • Ceramic or metal substrates eg honeycomb body
  • a noble metal solution e.g honeycomb body
  • the noble metal components can be applied to one or more oxides, fixed by calcining and then applied to the support as a catalytically active washcoat. In this case we speak of a one-step process. Precious metals in
  • Oxidation catalysts are often used, Pt, Pd, Au, Ag, Rh, Re, Ir, these precious metals are usually present as metal clusters.
  • the redox-active transition metals Mn, Fe and Cu are also frequently used in oxidation catalysts.
  • a disadvantage of the prior art is, inter alia, that the metal clusters lose their optimal activity due to an optimal cluster size in the course of their use by aging. That is, sintering the metal clusters of optimal size will form larger clusters with reduced active surface area.
  • the optimal size of the active metal clusters is usually much smaller than the average pore size of the washcoat, so the metal clusters therefore have enough room to grow above a certain temperature to the larger, less active clusters.
  • aging may also occur by a reduction in the accessible surface of the washcoat, for example, by conversion of the high surface area ⁇ ⁇ alumina to low surface area ⁇ -alumina. This reduces the accessibility of the reaction gases to the surface and decreases the activity of the catalyst.
  • zeolites form very stable structures, they can be damaged (for example, by de-aluminizing) under high temperatures, and in particular by the action of water vapor, which leads to a reduction in their internal surface and is accompanied by an activity reduction.
  • a further disadvantage of zeolites is that they usually have Bronsted acid centers which negatively affect the stability of the active metal clusters of oxidation state 0 which possess the highest activity for many oxidation reactions.
  • the object of the present invention was thus to obviate the disadvantages of the prior art, i.
  • the object is achieved by a method for producing metal-containing crystalline silicates, characterized in that a metal is introduced into a gallo, gallo-titanium, boron or boron-titanium silicate and the gallo, gallium titanium, boron or Boron-titanium silicate is calcined.
  • the metal exchange can be carried out without difficulty in the case of a gallium, gallium titanium, boron or boron-titanium silicate, since these have sufficient Bronsted acid centers because of the presence of gallium or boron.
  • gallo-, gallium-titanium, boron or boron-titanium silicates at temperatures above 600 0 C show a significant de-gelling or above 400 0 C a de-boronation, so that by a subsequent calcination the Bronsted acid centers can be removed and thus a stabilization of metal or noble metal of the oxidation state (0) is effected.
  • the metal is preferably introduced (exchanged) into the gallium, gallium titanium, boron or boron-titanium silicate via an aqueous ion exchange, an aqueous impregnation, an incipient wetness method or a solid-state exchange. These methods are known in the art.
  • the metal compound is introduced by impregnating the silicate material with a solution of the metal compound by means of pore volume impregnation.
  • the silicate material is brought into contact with an amount of solution whose volume corresponds to the pore volume of the silicate material used.
  • the introduction of the metal compound takes place by aqueous ion exchange.
  • the silicate material is suspended in water and mixed with a solution of the metal salt and stirred until all H + are replaced by M n + ions. Thereafter, the silicate is filtered off again and further processed, such as dried.
  • metal compounds transition metal compounds or noble metal compounds, the corresponding nitrates, acetates, oxalates, tartrates, formates, amines, sulfites,
  • Carbonates, halides or hydroxides can be used. It is also possible to use complex salts, such as M (NH 3 ) n m + salts, having the same anions.
  • the metal is preferably in a range of 0.1 to 15 wt .-%, more preferably 0.2 to 10 wt .-% and particularly preferably 0.5 to 8 wt .-% based on the total weight of the silicate in the Gallo -, Gallo-titanium, boron or boron-titanium silicate introduced.
  • the metal is preferably a precious metal or transition metal, more preferably selected from the group comprising Pt, Pd, Au, Ag, Rh, Re, Ir, Mn and / or Cu.
  • the calcination of the gallium, gallium titanium or boron or boron-titanium silicate is preferably carried out at temperatures above about 500 0 C, more preferably 500 to 900 0 C, in particular 550 to 700 0 C.
  • gallium or boron is removed from the crystal lattice.
  • Boron is already removed at temperatures above 400 0 C, preferably above 500 0 C, from the crystal lattice. This simultaneously removes the Bronsted acid centers from the crystal lattice, stabilizing the metal of the oxidation state (0). Clustering does not occur or only to a lesser extent.
  • a reduction with a reducing agent e.g. Hydrogen
  • a conversion of the metal compound into the corresponding metal i. into the catalytically active metal particles.
  • the invention also provides a crystalline silicate which has been prepared by the process described above.
  • the silicate is preferably a zeolitic, silicon-rich silicate, ie a silicate with a zeolite structure.
  • Suitable zeolitic silicate basic structures of gallo, gallo-titanium, boron or boron-titanium silicates in the context of this invention are selected from the topologies AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF, TONE and MFI, most preferably BEA, MFI, FER, MOR, MTW and CHA.
  • silicon-rich zeolites or crystalline silicates in the context of this invention zeolites or silicates are to be understood which have a Si / metal molar ratio of 10: 1 to 1500: 1, preferably 20: 1 to 100: 1.
  • zeolites in the context of the present invention are understood as meaning a crystalline substance from the group of aluminum silicates with a spatial network structure consisting of Si0 4 / A10 4 Tetrahedra are linked by common oxygen atoms to a regular three-dimensional network.
  • the zeolite structure contains voids, channels that are characteristic of each zeolite.
  • the zeolites are classified into different structures according to their topology.
  • the zeolite framework contains open cavities in the form of channels and cages that are normally occupied by water molecules and additional framework cations that can be exchanged.
  • An aluminum atom has an excess negative charge which is compensated by these cations.
  • the interior of the pore system represents the catalytically active surface. The more aluminum and the less silicon a zeolite contains, the denser the negative charge in its lattice and the more polar its internal surface.
  • the pore size and structure in addition to the parameters of manufacture, i. Use or type of templates, pH, pressure, temperature, presence of seed crystals, determined by the Si / Al ratio, which accounts for most of the catalytic character of a zeolite.
  • the presence of divalent or trivalent cations as a tetrahedral center in the zeolite framework gives the zeolite a negative charge in the form of so-called anion sites, in the vicinity of which the corresponding cation positions are located.
  • the negative charge is compensated by the incorporation of cations in the pores of the zeolite material.
  • Titanium silicalite TS-I (MFI structure) e.g. Although it is characterized by an extreme temperature stability of the grid, but an ion exchange is impossible.
  • the zeolites are mainly distinguished by the geometry of the cavities formed by the rigid network of SiO 4 / AlO 4 tetrahedra.
  • the entrances to the cavities are formed by 8, 10 or 12 rings, the expert speaks here of narrow, medium and large pore zeolites.
  • Certain zeolites show a uniform structure structure, e.g. For example, the ZSM-5 or the MFI topology, with linear or zigzag running channels, in others close behind the pore openings larger cavities, eg. As in the Y or A zeolites, with the topologies FAU and LTA.
  • Catalysts based on crystalline Galloaluminiumsilikate find especially in the petrochemical industry for the production of organic synthesis products. Due to their dehydration and cyclization properties, they are suitable for the conversion of lower hydrocarbons such as alkanes from liquefied petroleum gas (LPG) to aromatic hydrocarbons such as benzene, toluene or xylenes (so-called dehydrocyclodimerization).
  • LPG liquefied petroleum gas
  • aromatic hydrocarbons such as benzene, toluene or xylenes
  • zeolitic gallosilicates all aluminum atoms are replaced by gallium.
  • zeolitic boron silicates the aluminum atoms are correspondingly replaced by boron.
  • gallium titanium silicates the aluminum atoms are replaced by gallium and part of the silicon atoms are replaced by titanium.
  • boron-titanium silicates the aluminum atoms are replaced by boron and some of the silicon atoms are replaced by titanium.
  • the gallo-silicates used according to the invention can be obtained, for example, by hydrothermal crystallization of a synthesis gel.
  • a silicon source eg SiO 2
  • a gallium source eg GaCl 3
  • alkaline solution eg NaOH, NH 3
  • a structure-directing template for example of tetraalkylammonium compounds, usually proves advantageous.
  • a silicon-rich gallo-silicate is produced by a hydrothermal crystallization of a synthesis gel according to the invention.
  • the hydrothermal Crystallization carried out for 6 to 48 hours at a temperature of 100 to 250 0 C.
  • the hydrothermal crystallization is preferably carried out in the presence of an organic template.
  • Suitable templates are, for example, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide and tetraethylammonium bromide.
  • Silicon source eg SiO 2
  • a boron source eg BCl 3
  • Silicon source eg SiO 2
  • a boron source eg BCl 3
  • a template for example a tetraalkylammonium compound
  • a process for the preparation of boron silicates can be found, for example, in EP 0 534 200 A1.
  • the gallo-titanium silicate is prepared analogously to the gallo-silicate by hydrothermally crystallizing a gallium source, a titanium source, and a silicon source in the presence of a structure-directing agent.
  • a gallium source a gallium source
  • TiO 2 titanium source
  • SiO 2 silicon source
  • a structure-directing agent template
  • tetraalkylammonium compound for example
  • Suitable titanium-containing zeolite structures are e.g. MFI (TS-I) and other titanium silicates, for example ETS structures.
  • TS-I MFI
  • ETS-I tetraethylammonium
  • Temperatures of a maximum of 400 to 500 0 C is thermally treated.
  • the thermal treatment in this case causes a removal of the organic template components, without causing a de-Galliltechnik or de-boronation.
  • the invention thus also relates to a metal-containing crystalline silicate, wherein the metal is present in the silicate essentially in the oxidation state (0).
  • the metal-containing silicate is further characterized in that the silicate is substantially free of Bronsted acid centers.
  • the noble metal-containing silicate is further characterized in that it exhibits a signal in the IR spectrum for an adsorbed CO molecule at about 2088 ⁇ 15 cm -1 and at 2073 ⁇ 15 cm -1
  • the silicate according to the invention also shows vibration signals in the IR spectrum for CO at SiOH at 2156 ⁇ 15 cm -1 and for the Si-Ga at 2171 ⁇ 15 cm -1
  • the metal-containing silicate contains the metal in the range of 0.1 to 15 wt .-%, more preferably 0.2 to 10 wt .-% and particularly preferably 0.5 to 8 wt .-%, based on the total weight of the silicate.
  • Suitable zeolitic silicate basic structures of gallo, gallo-titanium, boron or boron-titanium silicates in the context of this invention are selected from the topologies AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF,
  • TON MFI and ETS, most preferably BEA, MFI, ETS, FER, MOR, MTW and CHA.
  • the metal-containing crystalline silicate according to the invention is either an aluminum-free silicate or zeolites rich in silicon.
  • silicon-rich zeolites in the context of this invention are meant zeolites having a Si / metal molar ratio of 10: 1 to 1500: 1, preferably 20: 1 to 500: 1.
  • aluminosilicates in which not all aluminum is replaced by gallium, boron and / or titanium for example galloaluminum silicates, boron-aluminum silicates and the like.
  • the invention also provides the use of the metal-containing silicate according to the invention as a high-temperature oxidation catalyst or as a diesel oxidation catalyst.
  • the metal-containing zeolite or the metal-containing crystalline silicate according to the invention is outstandingly suitable as a high-temperature oxidation catalyst, in particular as a result of its high temperature stability and due to the property that the metal does not tend to cluster Diesel oxidation catalyst.
  • the zeolitic structure When used as a diesel oxidation catalyst can also be exploited the advantage that the zeolitic structure also serves as a cold start trap for unburned hydrocarbons, which at low temperatures at which the
  • Oxidation efficiency of the catalyst is not yet high enough, adsorbed, and then at higher operating temperatures, i. be desorbed at optimal oxidation effect of the catalyst.
  • the invention further provides a catalytic composition containing the above-defined metal-containing crystalline silicate.
  • the catalytic composition preferably contains the metal-containing crystalline silicate in an amount of 5 to 70% by weight, more preferably 10 to 50%
  • Wt .-% particularly preferably from 15 to 50 wt .-% (based on the total mass of the catalytic composition).
  • the catalytic composition may further contain other metal oxides, binders, promoters, stabilizers and / or fillers.
  • the metal-containing crystalline silicate according to the invention or the catalytic composition containing the metal-containing crystalline silicate according to the invention can consequently be processed to form a washcoat which is suitable for coating catalyst supports or shaped catalyst bodies.
  • the washcoat comprises 5 to 70 wt .-%, more preferably 10 to 50 wt .-%, particularly preferably 15 to 50 wt .-% of the silicate according to the invention.
  • the invention thus also relates to a shaped catalyst body containing the inventive metal-containing crystalline silicate or the catalytic composition according to the invention.
  • the metal-containing crystalline silicate or the catalytic composition is particularly preferably present as a coating on the shaped catalyst body.
  • Ceramic shaped bodies which can be coated with the washcoat are, for example, ceramic or metallic honeycomb bodies (monoliths).
  • the application to the shaped catalyst body can be carried out by methods known in the art by dipping, spraying or the like.
  • the catalytic composition may also be processed into shaped articles such as tablets and extrudates in a known manner with the addition of suitable auxiliaries such as inorganic binders (e.g., silica sol), pore formers, plasticizers and humectants.
  • suitable auxiliaries such as inorganic binders (e.g., silica sol), pore formers, plasticizers and humectants.
  • the catalytic composition is applied in the form of a coating (as a washcoat) on the inner walls of the flow channels of metallic or ceramic honeycomb bodies (monoliths).
  • Coating amounts of 50 to 300 g / l volume of the honeycomb body advantageous. The necessary
  • the catalytic composition is processed into an aqueous coating dispersion.
  • This dispersion may be added as a binder, for example, silica sol.
  • the viscosity of the dispersion can be adjusted by suitable additives, so that it is possible, the required coating amount in a single operation on the Apply walls of the flow channels. If this is not possible, then the coating can be repeated several times, wherein the freshly applied coating is fixed in each case by an intermediate drying.
  • the finished coating is then dried at elevated temperature and calcined for a period of 1 to 4 hours at temperatures of 300 0 C to 600 0 C.
  • colloidal silica gel (6.615 g, containing 2.778 g of SiO 2 ) is charged with 1.723 g of tetrapropylammonium bromide (TPABr), 0.45 g of GaCl 3 solution (containing 0.067 g of gallium) and 3.238 g
  • Ga-TS-I Gallo-titanium Silicate
  • the product contains 2.2% platinum.
  • Fig. 3 shows an IR spectrum of the product after loading with carbon monoxide at 77 K, which is slowly rinsed with He.
  • the CO oscillations for CO on SiOH (2156 cm -1 ) and for Si-Ga at 2171 cm -1 can be seen. It can be clearly seen that after calcination at 550 ° C., there are still many Ga ions in the zeolite which still leave acidity in the zeolite.
  • Fig. 4 shows in the upper IR spectrum under CO at 20 mbar a signal at 2088 cm -1 which is associated with CO absorbed at Pt (0) cluster
  • the question of whether these are present in the zeolite can be determined by adding a strong Adamantanenitrile is so large that it does not get into the zeolite pores, so adsorption of adamantanenitrile before CO addition should strongly affect CO adsorption on large clusters outside the zeolite.
  • the lower spectrum in Fig. 4 shows the CO adsorption after adamantanenitrile adsorption.
  • the signals of the adsorbed adamantanenitrile can be recognized.
  • some CO molecules can be placed on the large clusters between the nitriles, bridging between 2 Pt atoms. These show a low absorption at 1868 cm -1 .
  • the main peak at 2073 cm '1 which can also be assigned to CO on Pt (O) clusters, has hardly decreased in intensity (Max. Adsorbance 0.85 versus 0.125), it can be concluded that a significant portion of the platinum atoms available for CO adsorption sit at the surface of clusters in the pores and are not blocked by adamantanitrile adsorption.
  • This Pt-Ga-TS-1 material can now be varied by calcination. If high hydrocarbon adsorption of the zeolite is desired for a hydrocarbon storage function in a DOC, the zeolite may be used after calcining at 550 ° C. If a very good CO oxidation is desired, a high tendency of the platinum to Pt (O) is necessary. Calcination above 600 ° C. (about 700 ° C.) requires a migration of the gallium from the lattice. As a result, the acid sites in the zeolite and the reoxidation tendency of the platinum are reduced, whereby, however, the storage capacity for hydrocarbons is reduced.
  • Fig. 5 shows a TGA-DSC (Thermogravimetric Analysis Differential Scanning Calorimetry) diagram of Ga-TS-I without platinum.
  • Titanium-silicalite TS-I is a well known extremely thermostable zeolite whose structure even after a thermal treatment above 1000 C 0 obese. Its preparation is described for example in US 4,410,501.
  • Platinum tetraminhydroxide solution (16.04% Pt) was added and stirred overnight.
  • the zeolite is filtered off and dried.
  • the powder is analyzed for Pt content and, according to analysis, contains less than 0.2% platinum, which shows that no ion exchange succeeds without Brönstedt acid sites.

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Abstract

The invention relates to novel metal-containing silicates, especially redox-active and crystalline silicates, to a process for preparing metal-containing crystalline silicates and to the use thereof as a high-temperature oxidation catalyst or diesel oxidation catalyst. The invention further relates to a catalytic composition and to a shaped catalyst body which comprises the metal-containing crystalline silicates.

Description

METHALLHALTIGE KRISTALLINE SILIKATE METHODOLOGICAL CRYSTALLINE SILICATES
Die Erfindung betrifft neuartige metallhaltige Silikate, insbesondere redoxaktive sowie kristalline Silikate, ein Verfahren zur Herstellung von metallhaltigen kristallinen Silikaten sowie deren Verwendung als Hochtemperaturoxidationskatalysator oderThe invention relates to novel metal-containing silicates, in particular redox-active and crystalline silicates, a process for the preparation of metal-containing crystalline silicates and their use as high-temperature oxidation catalyst or
Dieseloxidationskatalysator. Die Erfindung betrifft ferner eine katalytische Zusammensetzung sowie einenDiesel oxidation catalyst. The invention further relates to a catalytic composition and a
Katalysatorformkörper, der die metallhaltigen kristallinen Silikate enthält.Catalyst shaped body containing the metal-containing crystalline silicates.
Im Stand der Technik sind edelmetallhaltige Oxidationskatalysatoren für Abgasreinigungen sowohl in stationären als auch in mobilen Anwendungen bekannt. Üblicherweise werden als aktive Trägersubstanz Oxide oder Oxidmischungen, ausgewählt aus Al-, Ti-, Ce-, La, Zr-, Sn-, W- , Y-, Pr-, Gd-Oxiden und ggf. weiteren Erdalkalioxiden, eingesetzt. Diese Oxide werden gewöhnlich als Washcoat aufIn the prior art, noble metal-containing oxidation catalysts for emission control in both stationary and in mobile applications are known. Usually, oxides or oxide mixtures selected from Al, Ti, Ce, La, Zr, Sn, W, Y, Pr, Gd oxides and optionally further alkaline earth oxides are used as active carrier substance. These oxides usually become washcoat
Keramik- oder Metallsubstrate (z. B. Wabenkörper) aufgebracht und anschließend mit einer Edelmetalllösung imprägniert. Alternativ dazu können die Edelmetallkomponenten auf ein oder mehrere Oxide aufgebracht, durch eine Kalzinierung fixiert und anschließend als katalytisch aktiver Washcoat auf den Träger aufgebracht werden. In diesem Fall spricht man von einem Einschrittverfahren. Edelmetalle, die inCeramic or metal substrates (eg honeycomb body) applied and then impregnated with a noble metal solution. Alternatively, the noble metal components can be applied to one or more oxides, fixed by calcining and then applied to the support as a catalytically active washcoat. In this case we speak of a one-step process. Precious metals in
Oxidationskatalysatoren verwendet werden, sind häufig Pt, Pd, Au, Ag, Rh, Re, Ir, wobei diese Edelmetalle gewöhnlich als Metallcluster vorliegen.Oxidation catalysts are often used, Pt, Pd, Au, Ag, Rh, Re, Ir, these precious metals are usually present as metal clusters.
Außerdem werden häufig die redoxaktiven Übergangsmetalle Mn, Fe und Cu ebenfalls in Oxidationskatalysatoren verwendet. Nachteilig im Stand der Technik ist u.a., dass die Metallcluster ihre optimale Aktivität, bedingt durch eine optimale Clustergröße, im Laufe Ihres Einsatzes durch Alterung verlieren. Das heißt, durch eine Sinterung der Metallcluster optimaler Größe bilden sich größere Cluster mit verringerter aktiver Oberfläche. Die optimale Größe der aktiven Metallcluster ist normalerweise deutlich kleiner als die durchschnittliche Porengröße des Washcoats, wodurch die Metallcluster daher genügend Raum haben, um oberhalb einer bestimmten Temperatur zu den größeren, weniger aktiven Clustern anzuwachsen.In addition, the redox-active transition metals Mn, Fe and Cu are also frequently used in oxidation catalysts. A disadvantage of the prior art is, inter alia, that the metal clusters lose their optimal activity due to an optimal cluster size in the course of their use by aging. That is, sintering the metal clusters of optimal size will form larger clusters with reduced active surface area. The optimal size of the active metal clusters is usually much smaller than the average pore size of the washcoat, so the metal clusters therefore have enough room to grow above a certain temperature to the larger, less active clusters.
Eine Alterung kann jedoch auch durch eine Verringerung der zugänglichen Oberfläche des Washcoats, beispielsweise durch Umwandlung des oberflächenreichen γ~Aluminiumoxids zu oberflächenarmen α-Aluminiumoxids, ablaufen. Damit wird die Zugänglichkeit für die Reaktionsgase an die Oberfläche herabgesetzt und die Aktivität des Katalysators nimmt ab.However, aging may also occur by a reduction in the accessible surface of the washcoat, for example, by conversion of the high surface area γ ~ alumina to low surface area α-alumina. This reduces the accessibility of the reaction gases to the surface and decreases the activity of the catalyst.
Bekannt ist auch eine Deaktivierung des Katalysators durch Vergiftung, z.B. mit Schwefel, SiO2 oder anderen Katalysatorgiften.Also known is a deactivation of the catalyst by poisoning, for example with sulfur, SiO 2 or other catalyst poisons.
Im Stand der Technik wurden deshalb bereits mit Edelmetall beschichtete Zeolithe eingesetzt, um die Temperaturschädigung zu verringern. Obwohl Zeolithe sehr stabile Strukturen bilden, können sie unter hohen Temperaturen und insbesondere durch Einwirkung von Wasserdampf beschädigt werden (z.B. durch De- Aluminierung) , was zu einer Verminderung ihrer inneren Oberfläche führt und mit einer Aktivitätsminderung einhergeht.The prior art therefore used precious metal-coated zeolites in order to reduce the temperature damage. Although zeolites form very stable structures, they can be damaged (for example, by de-aluminizing) under high temperatures, and in particular by the action of water vapor, which leads to a reduction in their internal surface and is accompanied by an activity reduction.
Nachteilig bei Zeolithen ist ferner, dass diese gewöhnlich Brönsted-azide Zentren besitzen, die sich negativ auf die Stabilität der aktiven Metall-Cluster der Oxidationsstufe 0 auswirken, welche die höchste Aktivität für viele Oxidationsreaktionen besitzen.A further disadvantage of zeolites is that they usually have Bronsted acid centers which negatively affect the stability of the active metal clusters of oxidation state 0 which possess the highest activity for many oxidation reactions.
Es wäre deshalb vorteilhaft, alternative Verbindungen einzusetzen, die bei hohen Temperaturen stabil sind und eine Clusterbildung der Metalle verhindern.It would therefore be advantageous to use alternative compounds that are stable at high temperatures and prevent clustering of the metals.
Die Aufgabe der vorliegenden Erfindung bestand somit darin, die Nachteile des Standes der Technik zu umgehen, d.h. ein hochtemperaturstabiles kristallines Silikat mit einer hohen Metallbeladung bereitzustellen, bei dem der Metalleintausch leicht durchführbar ist, aber die Clusterbildung der Metalle weitestgehend vermieden wird.The object of the present invention was thus to obviate the disadvantages of the prior art, i. To provide a high temperature stable crystalline silicate with a high metal loading, in which the metal exchange is easy to carry out, but the clustering of the metals is largely avoided.
Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung von metallhaltigen kristallinen Silikaten, dadurch gekennzeichnet, dass ein Metall in ein Gallo-, Gallo-Titan, Bor- oder Bor-Titan-Silikat eingebracht und das Gallo-, Gallo- Titan, Bor- oder Bor-Titan-Silikat kalziniert wird.The object is achieved by a method for producing metal-containing crystalline silicates, characterized in that a metal is introduced into a gallo, gallo-titanium, boron or boron-titanium silicate and the gallo, gallium titanium, boron or Boron-titanium silicate is calcined.
Überraschenderweise wurde gefunden, dass der Metalleintausch bei einem Gallo-, Gallo-Titan, Bor- oder Bor-Titan-Silikat problemlos durchgeführt werden kann, da diese wegen der Anwesenheit von Gallium oder Bor über ausreichend Brönsted- azide Zentren verfügen. Ebenfalls überraschend wurde gefunden, dass Gallo-, Gallo-Titan, Bor- oder Bor-Titan-Silikate bei Temperaturen oberhalb von 6000C eine deutliche De-GaIliierung bzw. oberhalb von 4000C eine De-Borierung zeigen, so dass durch eine nachfolgende Kalzinierung die Brönsted-aziden Zentren entfernt werden können und somit eine Stabilisierung von Metall oder Edelmetall der Oxidationsstufe (0) bewirkt wird. Bevorzugt wird das Metall in das Gallo-, Gallo-Titan, Boroder Bor-Titan-Silikat über einen wässrigen Ionenaustausch, eine wässrige Imprägnierung, eine Incipient-Wetness-Methode oder .einen Festkörperaustausch eingebracht (eingetauscht) . Diese Verfahren sind im Stand der Technik bekannt.Surprisingly, it has been found that the metal exchange can be carried out without difficulty in the case of a gallium, gallium titanium, boron or boron-titanium silicate, since these have sufficient Bronsted acid centers because of the presence of gallium or boron. Also surprisingly, it was found that gallo-, gallium-titanium, boron or boron-titanium silicates at temperatures above 600 0 C show a significant de-gelling or above 400 0 C a de-boronation, so that by a subsequent calcination the Bronsted acid centers can be removed and thus a stabilization of metal or noble metal of the oxidation state (0) is effected. The metal is preferably introduced (exchanged) into the gallium, gallium titanium, boron or boron-titanium silicate via an aqueous ion exchange, an aqueous impregnation, an incipient wetness method or a solid-state exchange. These methods are known in the art.
Gemäß einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt das Einbringen der Metallverbindung durch Imprägnieren des Silikatmaterials mit einer Lösung der Metallverbindung mittels Porenvolumenimprägnierung . Dabei wird das Silikatmaterial mit einer Menge an Lösung in Kontakt gebracht, deren Volumen dem Porenvolumen des eingesetzten Silikatmaterials entspricht.According to a preferred embodiment of the method according to the invention, the metal compound is introduced by impregnating the silicate material with a solution of the metal compound by means of pore volume impregnation. In this case, the silicate material is brought into contact with an amount of solution whose volume corresponds to the pore volume of the silicate material used.
Gemäß einer weiteren bevorzugten Ausführungsform erfolgt das Einbringen der MetallVerbindung durch wässrigen Ionenaustausch. Dabei wird das Silikatmaterial in Wasser suspendiert und mit einer Lösung des Metallsalzes versetzt und so lange gerührt, bis alle H+ gegen Mn+-Ionen ausgetauscht sind. Danach wird das Silikat wieder abfiltriert und weiter verarbeitet, wie z.B. getrocknet.According to a further preferred embodiment, the introduction of the metal compound takes place by aqueous ion exchange. The silicate material is suspended in water and mixed with a solution of the metal salt and stirred until all H + are replaced by M n + ions. Thereafter, the silicate is filtered off again and further processed, such as dried.
Als Metallverbindungen, Übergangsmetallverbindungen bzw. Edelmetallverbindungen, können die entsprechenden Nitrate, Acetate, Oxalate, Tartrate, Formiate, Amine, Sulfite,As metal compounds, transition metal compounds or noble metal compounds, the corresponding nitrates, acetates, oxalates, tartrates, formates, amines, sulfites,
Carbonate, Halogenide oder Hydroxide eingesetzt werden. Es können auch Komplexsalze, wie M (NH3) n m+-Salze mit den gleichen Anionen eingesetzt werden.Carbonates, halides or hydroxides can be used. It is also possible to use complex salts, such as M (NH 3 ) n m + salts, having the same anions.
Das Metall wird bevorzugt in einem Bereich von 0,1 bis 15 Gew.-%, mehr bevorzugt 0,2 bis 10 Gew.-% und besonders bevorzugt 0,5 bis 8 Gew.-% bezogen auf das Gesamtgewicht des Silikats in das Gallo-, Gallo-Titan, Bor- oder Bor-Titan- Silikat eingebracht. Das Metall ist bevorzugt ein Edelmetall oder Übergangsmetall, besonders bevorzugt ausgewählt aus der Gruppe umfassend Pt, Pd, Au, Ag, Rh, Re, Ir, Mn und/oder Cu.The metal is preferably in a range of 0.1 to 15 wt .-%, more preferably 0.2 to 10 wt .-% and particularly preferably 0.5 to 8 wt .-% based on the total weight of the silicate in the Gallo -, Gallo-titanium, boron or boron-titanium silicate introduced. The metal is preferably a precious metal or transition metal, more preferably selected from the group comprising Pt, Pd, Au, Ag, Rh, Re, Ir, Mn and / or Cu.
Das Kalzinieren des Gallo-, Gallo-Titan oder Bor- oder Bor- Titan-Silikats erfolgt vorzugsweise bei Temperaturen oberhalb von etwa 500 0C, besonders bevorzugt 500 bis 900 0C, insbesondere 550 bis 700 0C. Durch Kalzinieren über 6000C wird Gallium oder Bor aus dem Kristallgitter entfernt. Bor wird bereits bei Temperaturen oberhalb 400 0C, bevorzugt oberhalb 500 0C, aus dem Kristallgitter entfernt. Dadurch werden gleichzeitig die Brönsted-aziden Zentren aus dem Kristallgitter entfernt, so dass das Metall der Oxidationsstufe (0) stabilisiert wird. Eine Clusterbildung tritt nicht oder nur in vermindertem Umfang auf .The calcination of the gallium, gallium titanium or boron or boron-titanium silicate is preferably carried out at temperatures above about 500 0 C, more preferably 500 to 900 0 C, in particular 550 to 700 0 C. By calcination above 600 0 C. gallium or boron is removed from the crystal lattice. Boron is already removed at temperatures above 400 0 C, preferably above 500 0 C, from the crystal lattice. This simultaneously removes the Bronsted acid centers from the crystal lattice, stabilizing the metal of the oxidation state (0). Clustering does not occur or only to a lesser extent.
Erfindungsgemäß ist es ferner bevorzugt, dass nach dem Kalzinieren eine Reduktion mit einem Reduktionsmittel, z.B. Wasserstoff, erfolgt. Dabei erfolgt eine Umwandlung der Metallverbindung in das entsprechende Metall, d.h. in die katalytisch aktiven Metallpartikel.According to the invention, it is further preferred that after calcining, a reduction with a reducing agent, e.g. Hydrogen, takes place. In this case, a conversion of the metal compound into the corresponding metal, i. into the catalytically active metal particles.
Gegenstand der Erfindung ist auch ein kristallines Silikat, das nach dem oben beschriebenen Verfahren hergestellt wurde.The invention also provides a crystalline silicate which has been prepared by the process described above.
Bei dem Silikat im Sinne dieser Erfindung handelt es sich bevorzugt um ein zeolithisches, siliziumreiches Silikat, also um ein Silikat mit Zeolithstruktur .For the purposes of this invention, the silicate is preferably a zeolitic, silicon-rich silicate, ie a silicate with a zeolite structure.
Geeignete zeolithische Silikat-Grundstrukturen der Gallo-, Gallo-Titan, Bor- oder Bor-Titan-Silikate im Sinne dieser Erfindung sind ausgewählt aus den Topologien AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF, TON und MFI, ganz besonders bevorzugt BEA, MFI, FER, MOR, MTW und CHA. Als siliziumreiche Zeolithe bzw. kristalline Silikate im Sinne dieser Erfindung sollen Zeolithe bzw. Silikate verstanden werden, die ein Si/Metall-Molverhältnis von 10:1 bis 1500:1, vorzugsweise 20:1 bis 100:1 besitzen.Suitable zeolitic silicate basic structures of gallo, gallo-titanium, boron or boron-titanium silicates in the context of this invention are selected from the topologies AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF, TONE and MFI, most preferably BEA, MFI, FER, MOR, MTW and CHA. As silicon-rich zeolites or crystalline silicates in the context of this invention, zeolites or silicates are to be understood which have a Si / metal molar ratio of 10: 1 to 1500: 1, preferably 20: 1 to 100: 1.
Zeolithe im Rahmen der vorliegenden Erfindung sind gemäß der Definition der International Mineralical Association (D.S. Coombs et al . , Canadian Mineralogist, 35, 1979, 1571) eine kristalline Substanz aus der Gruppe der Aluminiumsilikate mit einer Raumnetzstruktur verstanden, die aus Si04/A104.Tetraeder bestehen, die durch gemeinsame Sauerstoffatome zu einem regelmäßigen dreidimensionalen Netzwerk verknüpft sind.According to the definition of the International Mineralical Association (DS Coombs et al., Canadian Mineralogist, 35, 1979, 1571), zeolites in the context of the present invention are understood as meaning a crystalline substance from the group of aluminum silicates with a spatial network structure consisting of Si0 4 / A10 4 Tetrahedra are linked by common oxygen atoms to a regular three-dimensional network.
Die Zeolithstruktur enthält Hohlräume, Kanäle, die für jeden Zeolithen charakteristisch sind. Die Zeolithe werden gemäß ihrer Topologie in verschiedene Strukturen eingeteilt. Das Zeolithgerüst enthält offene Hohlräume in Form von Kanälen und Käfigen, die normalerweise mit Wassermolekülen und zusätzlichen Gerüstkationen besetzt sind, die ausgetauscht werden können. Auf ein Aluminiumatom kommt eine überschüssige negative Ladung, die durch diese Kationen kompensiert wird. Das Innere des Porensystems stellt die katalytisch aktive Oberfläche dar. Je mehr Aluminium und je weniger Silizium ein Zeolith enthält, desto dichter ist die negative Ladung in seinem Gitter und desto polarer seine innere Oberfläche. Die Porengröße und Struktur wird neben den Parametern bei der Herstellung, d.h. Verwendung bzw. Art von Templaten, pH, Druck, Temperatur, Anwesenheit von Impfkristallen, durch das Si/Al-Verhältnis bestimmt, das den größten Teil des katalytischen Charakters eines Zeolithen ausmacht.The zeolite structure contains voids, channels that are characteristic of each zeolite. The zeolites are classified into different structures according to their topology. The zeolite framework contains open cavities in the form of channels and cages that are normally occupied by water molecules and additional framework cations that can be exchanged. An aluminum atom has an excess negative charge which is compensated by these cations. The interior of the pore system represents the catalytically active surface. The more aluminum and the less silicon a zeolite contains, the denser the negative charge in its lattice and the more polar its internal surface. The pore size and structure, in addition to the parameters of manufacture, i. Use or type of templates, pH, pressure, temperature, presence of seed crystals, determined by the Si / Al ratio, which accounts for most of the catalytic character of a zeolite.
Durch Anwesenheit von zwei- oder dreiwertigen Kationen als Tetraederzentrum im Zeolithgerüst erhält der Zeolith eine negative Ladung in Form von sog. Anionenstellen, in deren Nachbarschaft sich die entsprechenden Kationenpositionen befinden. Die negative Ladung wird durch den Einbau von Kationen in die Poren des Zeolithmaterials kompensiert.The presence of divalent or trivalent cations as a tetrahedral center in the zeolite framework gives the zeolite a negative charge in the form of so-called anion sites, in the vicinity of which the corresponding cation positions are located. The negative charge is compensated by the incorporation of cations in the pores of the zeolite material.
In einem reinen nicht-Ionenausgetauschten Zeolithen sind das in der Regel H+-Ionen, die Brönsted-saure-Eigenschaften induzieren, aber auch gegen andere Mn+-Ionen im Gitter ausgetauscht werden können. Bei den klassischen Al-haltigen Zeolithen sind diese dreiwertigen Kationen, die Brönsted- Azidität induzieren, Al3+-Ionen. Dementsprechend enthalten reine Silikate und Titan-Silikate keine Brönsted-Azidität und keine Möglichkeit H+-Ionen gegen andere Ionen auszutauschen.In a pure non-ion-exchanged zeolite, these are usually H + ions that induce Brönsted acidic properties but can also be exchanged for other Mn + ions in the lattice. In the classical Al-containing zeolites, these trivalent cations that induce Brönsted acidity are Al 3+ ions. Accordingly, pure silicates and titanium silicates contain no Brönsted acidity and no possibility to exchange H + ions for other ions.
Titan-Silikalit TS-I (MFI-Struktur) z.B. zeichnet sich zwar durch eine extreme Temperaturstabilität des Gitters aus, aber ein Ionenaustausch ist unmöglich.Titanium silicalite TS-I (MFI structure) e.g. Although it is characterized by an extreme temperature stability of the grid, but an ion exchange is impossible.
Die Zeolithe unterscheidet man hauptsächlich nach der Geometrie der Hohlräume, die durch das starre Netzwerk der SiO4/AlO4-Tetraeder gebildet werden. Die Eingänge zu den Hohlräumen werden von 8, 10 oder 12 Ringen gebildet, der Fachmann spricht hier von eng-, mittel- und weitporigen Zeolithen. Bestimmte Zeolithe zeigen einen gleichförmigen Strukturaufbau, z. B. die ZSM-5- oder die MFI-Topologie, mit linearen oder Zickzack- förmig verlaufenden Kanälen, bei anderen schließen sich hinter den Porenöffnungen größere Hohlräume an, z. B. bei den Y- oder A-Zeolithen, mit den Topologien FAU und LTA.The zeolites are mainly distinguished by the geometry of the cavities formed by the rigid network of SiO 4 / AlO 4 tetrahedra. The entrances to the cavities are formed by 8, 10 or 12 rings, the expert speaks here of narrow, medium and large pore zeolites. Certain zeolites show a uniform structure structure, e.g. For example, the ZSM-5 or the MFI topology, with linear or zigzag running channels, in others close behind the pore openings larger cavities, eg. As in the Y or A zeolites, with the topologies FAU and LTA.
In kristallinen Galloaluminiumsilikaten sind neben Silizium- und Aluminiumatomen auch dreiwertige Galliumatome in das Gitter eingebaut. Tetraeder aus Sauerstoffatomen bilden ein definiertes Hohlraumsystem mit Kanälen und Poren, wobei die charakteristischen Eigenschaften des Zeolithen durch die Größe und die Anzahl dieser Poren definiert werden.In crystalline Galloaluminiumsilikaten in addition to silicon and aluminum atoms and trivalent gallium atoms are incorporated into the lattice. Tetrahedra of oxygen atoms form a defined cavity system with channels and pores, wherein the Characteristic properties of the zeolite can be defined by the size and number of these pores.
Katalysatoren auf Basis kristalliner Galloaluminiumsilikate finden vor allem Anwendung in der petrochetnischen Industrie zur Herstellung organischer Syntheseprodukte. Aufgrund ihrer Dehydrierungs- und Zyklisierungseigenschaften eignen sie sich zur Umwandlung niederer Kohlenwasserstoffe wie Alkane aus verflüssigtem Petrolgas (LPG) zu aromatischen Kohlenwasserstoffen wie Benzol, Toluol oder Xylolen (sogenannte Dehydrozyklodimerisierung) .Catalysts based on crystalline Galloaluminiumsilikate find especially in the petrochemical industry for the production of organic synthesis products. Due to their dehydration and cyclization properties, they are suitable for the conversion of lower hydrocarbons such as alkanes from liquefied petroleum gas (LPG) to aromatic hydrocarbons such as benzene, toluene or xylenes (so-called dehydrocyclodimerization).
In zeolithischen Gallosilikaten sind hingegen alle Aluminiumatome durch Gallium ersetzt. In zeolithischen BorSilikaten sind entsprechend die Aluminiumatome durch Bor ersetzt. In Gallo-Titan-Silikaten sind die Aluminiumatome durch Gallium und ein Teil der Siliziumatome gegen Titan ersetzt. In Bor-Titan-Silikaten sind die Aluminiumatome durch Bor und ein Teil der Siliziumatome gegen Titan ersetzt.In zeolitic gallosilicates, however, all aluminum atoms are replaced by gallium. In zeolitic boron silicates, the aluminum atoms are correspondingly replaced by boron. In gallium titanium silicates, the aluminum atoms are replaced by gallium and part of the silicon atoms are replaced by titanium. In boron-titanium silicates, the aluminum atoms are replaced by boron and some of the silicon atoms are replaced by titanium.
Die erfindungsgemäß eingesetzten Gallo-Silikate können beispielsweise durch hydrothermale Kristallisation eines Synthesegels erhalten werden. Dazu wird gewöhnlich eine Siliziumquelle (z.B. SiO2) und eine Galliumquelle (z.B. GaCl3) in alkalischer Lösung (z.B. NaOH, NH3) mehrere Tage kristallisiert. Als vorteilhaft erweist sich meist die Zugabe eines strukturdirigierenden Templats, beispielsweise von Tetraalkylammoniumverbindungen .The gallo-silicates used according to the invention can be obtained, for example, by hydrothermal crystallization of a synthesis gel. Usually a silicon source (eg SiO 2 ) and a gallium source (eg GaCl 3 ) are crystallized in alkaline solution (eg NaOH, NH 3 ) for several days. The addition of a structure-directing template, for example of tetraalkylammonium compounds, usually proves advantageous.
Verfahren zur Herstellung von Gallo-Silikaten sind beispielsweise im US 5,466,432 beschrieben. In Anlehnung daran wird erfindungsgemäß ein siliziumreiches Gallo-Silikat durch eine hydrothermale Kristallisation eines Synthesegels hergestellt. Vorzugsweise wird die hydrothermale Kristallisation über 6 bis 48 Stunden bei einer Temperatur von 100 bis 2500C durchgeführt.Processes for the preparation of gallo-silicates are described, for example, in US Pat. No. 5,466,432. In accordance with the invention, a silicon-rich gallo-silicate is produced by a hydrothermal crystallization of a synthesis gel according to the invention. Preferably, the hydrothermal Crystallization carried out for 6 to 48 hours at a temperature of 100 to 250 0 C.
Bevorzugt wird wie schon gesagt die hydrothermale Kristallisation in Gegenwart eines organischen Templats durchgeführt. Geeignete Template sind beispielsweise Tetrapropylammoniumhydroxid, Tetrapropylammoniumbromid, Tetraethylammoniumhydroxid und Tetraethylammoniumbromid.As already mentioned, the hydrothermal crystallization is preferably carried out in the presence of an organic template. Suitable templates are, for example, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide and tetraethylammonium bromide.
Der Zugang zu Bor-Silikaten erfolgt analog, indem eineAccess to boron silicates is analogous by a
Siliziumquelle (z.B. SiO2) und eine Borquelle (z.B. BCl3) in alkalischer Lösung einer hydrothermalen Kristallisation ausgesetzt werden. Auch hier ist die Verwendung eines Templats, z.B. eine Tetraalkylammoniumverbindung, vorteilhaft. Ein Verfahren zur Herstellung von Bor-Silikaten findet sich beispielsweise in der EP 0 534 200 Al.Silicon source (eg SiO 2 ) and a boron source (eg BCl 3 ) are exposed in an alkaline solution of a hydrothermal crystallization. Again, the use of a template, for example a tetraalkylammonium compound, is advantageous. A process for the preparation of boron silicates can be found, for example, in EP 0 534 200 A1.
Das Gallo-Titan-Silikat wird in analoger Weise zum Gallo- Silikat hergestellt, indem eine Galliumquelle, eine Titanquelle und eine Siliziumquelle in Gegenwart eines strukturdirigierenden Agens hydrothermal kristallisiert werden. Als Galliumquelle kann z.B. Ga2O3, als Titanquelle TiO2 und als Siliziumquelle SiO2 eingesetzt werden. Als strukturdirigierenden Agens (Templat) kann wiederum eine Tetraalkylammoniumverbindung dienen, beispielsweiseThe gallo-titanium silicate is prepared analogously to the gallo-silicate by hydrothermally crystallizing a gallium source, a titanium source, and a silicon source in the presence of a structure-directing agent. For example, Ga 2 O 3 can be used as gallium source, TiO 2 as titanium source and SiO 2 as silicon source. As a structure-directing agent (template) can in turn serve a tetraalkylammonium compound, for example
Tetrapropylammoniumhydroxid, Tetrapropylammoniumbromid, Tetraethylammoniumhydroxid und Tetraethylammoniumbromid. Geeignete Titan-haltige Zeolithstrukturen sind z.B. MFI (TS-I) und andere Titan-Silikate, beispielsweise ETS-Strukturen. Die Synthese des Bor-Titan-Silikats erfolgt analog, jedoch mit einer Borquelle anstelle einer Galliumquelle.Tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide and tetraethylammonium bromide. Suitable titanium-containing zeolite structures are e.g. MFI (TS-I) and other titanium silicates, for example ETS structures. The synthesis of boron-titanium silicate is analogous, but with a boron source instead of a gallium source.
Bei der Verwendung von organischen Templaten ist es erforderlich, dass diese im Anschluss an die Zeolithsynthese bzw. Silikatsynthese wieder entfernt werden. Dies erfolgt gewöhnlich durch Herausbrennen des Templats bei Temperaturen von oberhalb 400 0C, bevorzugt 400 bis 500 0C. Dabei muss erfindungsgemäß darauf geachtet werden, dass es zu keiner De- Galliierung oder De-Borierung kommt. Dies kann beispielsweise durch Kontrolle über NH4TPD (Temperaturprogrammierte Ammonium- Desorption) erfolgen. In dem erfindungsgemäßen Verfahren ist es somit bevorzugt, dass vor dem Einbringen des Metalls in das Gallo-Silikat, Gallo-Titan-Silikat , Bor-Silikat oder Bor- Titan-Silikat das entsprechende Ausgangssilikat beiThe use of organic templates requires that these be followed by zeolite synthesis or silicate synthesis are removed again. This is usually done by burning out the template at temperatures above 400 0 C, preferably 400 to 500 0 C. It must be ensured according to the invention that there is no de-Galliierung or de-boronation. This can be done, for example, by controlling NH 4 TPD (Temperature Programmed Ammonium Desorption). In the method according to the invention, it is thus preferred that the corresponding starting silicate is present before the introduction of the metal into the gallo-silicate, gallo-titanium silicate, boron-silicate or boron-titanium silicate
Temperaturen von maximal 400 bis 500 0C thermisch behandelt wird. Die thermische Behandlung bewirkt hierbei ein Entfernen der organischen Templat-Komponenten, ohne eine De-Gallilierung oder De-Borierung herbeizuführen.Temperatures of a maximum of 400 to 500 0 C is thermally treated. The thermal treatment in this case causes a removal of the organic template components, without causing a de-Gallilierung or de-boronation.
Erst danach erfolgt der Metalleintausch und die Kalzinierung wie oben beschrieben und führt so zu den erfindungsgemäßen metallhaltigen Silikaten.Only then does the metal exchange and the calcining take place as described above and thus leads to the metal-containing silicates according to the invention.
Gegenstand der Erfindung ist somit auch ein metallhaltiges kristallines Silikat, wobei das Metall in dem Silikat im Wesentlichen in der Oxidationsstufe (0) vorliegt. Im Wesentlichen bedeutet dabei zu mehr als 90 %, bevorzugt mehr als 95 %, besonders bevorzugt mehr als 99 % liegt das Metall in der Oxidationsstufe (0) vor.The invention thus also relates to a metal-containing crystalline silicate, wherein the metal is present in the silicate essentially in the oxidation state (0). In this case, essentially more than 90%, preferably more than 95%, particularly preferably more than 99%, is the metal in the oxidation state (0).
Das metallhaltige Silikat ist ferner dadurch gekennzeichnet, dass das Silikat im Wesentlichen frei von Brönsted-aziden Zentren ist. Das edelmetallhaltige Silikat ist weiter dadurch gekennzeichnet, dass es ein Signal im IR-Spektrum für ein adsorbiertes CO-Molekül bei etwa 2088 ± 15 cm"1 und bei 2073 ± 15 cm'1 zeigt. Das erfindungsgemäße Silikat zeigt ferner im IR- Spektrum Schwingungsignale für CO an SiOH bei 2156 ± 15 cm"1 und für die Si-Ga Schwingung bei 2171 ± 15 cm -1 Das metallhaltige Silikat enthält das Metall im Bereich von 0,1 bis 15 Gew.-%, mehr bevorzugt 0,2 bis 10 Gew.-% und besonders bevorzugt 0,5 bis 8 Gew.-%, bezogen auf das Gesamtgewicht des Silikats.The metal-containing silicate is further characterized in that the silicate is substantially free of Bronsted acid centers. The noble metal-containing silicate is further characterized in that it exhibits a signal in the IR spectrum for an adsorbed CO molecule at about 2088 ± 15 cm -1 and at 2073 ± 15 cm -1 The silicate according to the invention also shows vibration signals in the IR spectrum for CO at SiOH at 2156 ± 15 cm -1 and for the Si-Ga at 2171 ± 15 cm -1 The metal-containing silicate contains the metal in the range of 0.1 to 15 wt .-%, more preferably 0.2 to 10 wt .-% and particularly preferably 0.5 to 8 wt .-%, based on the total weight of the silicate.
Geeignete zeolithische Silikat-Grundstrukturen der Gallo-, Gallo-Titan, Bor- oder Bor-Titan-Silikate im Sinne dieser Erfindung sind ausgewählt aus den Topologien AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF,Suitable zeolitic silicate basic structures of gallo, gallo-titanium, boron or boron-titanium silicates in the context of this invention are selected from the topologies AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF,
TON, MFI und ETS, ganz besonders bevorzugt BEA, MFI, ETS, FER, MOR, MTW und CHA.TON, MFI and ETS, most preferably BEA, MFI, ETS, FER, MOR, MTW and CHA.
Bei dem erfindungsgemäßen metallhaltigen kristallinen Silikat handelt es sich entweder um ein aluminiumfreies Silikat, oder um siliziumreiche Zeolithe. Als siliziumreiche Zeolithe im Sinne dieser Erfindung sollen Zeolithe verstanden werden, die ein Si/Metall-Molverhältnis von 10:1 bis 1500:1, vorzugsweise 20:1 bis 500:1 besitzen. Bevorzugt im Sinne dieser Erfindung sind ferner Alumosilikate, bei denen nicht alles Aluminium durch Gallium, Bor und/oder Titan ersetzt ist, beispielsweise Gallo-Aluminium-Silikate, Bor-Aluminium-Silikate und dergleichen.The metal-containing crystalline silicate according to the invention is either an aluminum-free silicate or zeolites rich in silicon. As silicon-rich zeolites in the context of this invention are meant zeolites having a Si / metal molar ratio of 10: 1 to 1500: 1, preferably 20: 1 to 500: 1. Also preferred for the purposes of this invention are aluminosilicates in which not all aluminum is replaced by gallium, boron and / or titanium, for example galloaluminum silicates, boron-aluminum silicates and the like.
Gegenstand der Erfindung ist auch die Verwendung des erfindungsgemäßen metallhaltigen Silikats als Hochtemperaturoxidationskatalysator oder als Dieseloxidationskatalysator .The invention also provides the use of the metal-containing silicate according to the invention as a high-temperature oxidation catalyst or as a diesel oxidation catalyst.
Der erfindungsgemäße metallhaltige Zeolith bzw. das metallhaltige kristalline Silikat eignet sich aufgrund seiner hohen Temperaturstabilität und aufgrund der Eigenschaft, dass das Metall nicht zur Clusterbildung neigt, hervorragend als Hochtemperaturoxidationskatalysator, insbesondere als Dieseloxidationskatalysator. Bei der Verwendung als Dieseloxidationskatalysator kann weiterhin der Vorteil ausgenutzt werden, dass die zeolithische Struktur gleichzeitig als Kaltstartfalle für unverbrannte Kohlenwasserstoffe dient, die bei niedrigen Temperaturen, bei denen dieThe metal-containing zeolite or the metal-containing crystalline silicate according to the invention is outstandingly suitable as a high-temperature oxidation catalyst, in particular as a result of its high temperature stability and due to the property that the metal does not tend to cluster Diesel oxidation catalyst. When used as a diesel oxidation catalyst can also be exploited the advantage that the zeolitic structure also serves as a cold start trap for unburned hydrocarbons, which at low temperatures at which the
Oxidationswirkung des Katalysators noch nicht hoch genug ist, adsorbiert werden, und dann bei höheren Betriebstemperaturen, d.h. bei optimaler Oxidationswirkung des Katalysators, desorbiert werden.Oxidation efficiency of the catalyst is not yet high enough, adsorbed, and then at higher operating temperatures, i. be desorbed at optimal oxidation effect of the catalyst.
Gegenstand der Erfindung ist ferner eine katalytische Zusammensetzung, die das oben definierte metallhaltige kristalline Silikat enthält. Die katalytische Zusammensetzung enthält das metallhaltige kristalline Silikat vorzugsweise in einer Menge von 5 bis 70 Gew.-%, mehr bevorzugt 10 bis 50The invention further provides a catalytic composition containing the above-defined metal-containing crystalline silicate. The catalytic composition preferably contains the metal-containing crystalline silicate in an amount of 5 to 70% by weight, more preferably 10 to 50%
Gew.-%, besonders bevorzugt von 15 bis 50 Gew.-% (bezogen auf die Gesamtmasse der katalytischen Zusammensetzung) .Wt .-%, particularly preferably from 15 to 50 wt .-% (based on the total mass of the catalytic composition).
Die katalytische Zusammensetzung kann ferner weitere Metalloxide, Binder, Promotoren, Stabilisatoren und/oder Füllstoffe enthalten.The catalytic composition may further contain other metal oxides, binders, promoters, stabilizers and / or fillers.
Das erfindungsgemäße metallhaltige kristalline Silikat bzw. die katalytische Zusammensetzung, welche das erfindungsgemäße metallhaltige kristalline Silikat enthält, kann folglich zu einem Washcoat verarbeitet werden, der zur Beschichtung von Katalysatorträgern oder Katalysatorformkörpern geeignet ist . Vorzugsweise umfasst der Washcoat 5 bis 70 Gew.-%, mehr bevorzugt 10 bis 50 Gew.-%, besonders bevorzugt 15 bis 50 Gew.-% des erfindungsgemäßen Silikats.The metal-containing crystalline silicate according to the invention or the catalytic composition containing the metal-containing crystalline silicate according to the invention can consequently be processed to form a washcoat which is suitable for coating catalyst supports or shaped catalyst bodies. Preferably, the washcoat comprises 5 to 70 wt .-%, more preferably 10 to 50 wt .-%, particularly preferably 15 to 50 wt .-% of the silicate according to the invention.
Gegenstand der Erfindung ist somit auch ein Katalysatorformkörper, enthaltend das erfindungsgemäße metallhaltige kristalline Silikat bzw. die erfindungsgemäße katalytische Zusammensetzung.The invention thus also relates to a shaped catalyst body containing the inventive metal-containing crystalline silicate or the catalytic composition according to the invention.
Besonders bevorzugt liegt das metallhaltige kristalline Silikat oder die katalytische Zusammensetzung als Beschichtung auf dem Katalysatorformkörper vor .The metal-containing crystalline silicate or the catalytic composition is particularly preferably present as a coating on the shaped catalyst body.
Als Katalysatorformkörper, die mit dem Washcoat beschichtet werden können, eignen sich beispielsweise keramische oder metallische Wabenkörper (Monolithe) . Die Aufbringung auf den Katalysatorformkörper kann nach im Stand der Technik bekannten Methoden durch Tauchen, Sprühen oder dergleichen durchgeführt werden .Ceramic shaped bodies which can be coated with the washcoat are, for example, ceramic or metallic honeycomb bodies (monoliths). The application to the shaped catalyst body can be carried out by methods known in the art by dipping, spraying or the like.
Alternativ dazu kann die katalytische Zusammensetzung auch unter Zusatz geeigneter Hilfsstoffe wie anorganischen Bindern (z.B. Silicasol) , Porenbildnern, Plastifiziermitteln und Befeuchtungsmitteln in bekannter Weise zu Formkörpern wie Tabletten und Extrudaten verarbeitet werden. Bevorzugt wird die katalytische Zusammensetzung jedoch in Form einer Beschichtung (als Washcoat) auf den Innenwandungen der Strömungskanäle von metallischen oder keramischen Wabenkörpern (Monolithe) aufgebracht.Alternatively, the catalytic composition may also be processed into shaped articles such as tablets and extrudates in a known manner with the addition of suitable auxiliaries such as inorganic binders (e.g., silica sol), pore formers, plasticizers and humectants. Preferably, however, the catalytic composition is applied in the form of a coating (as a washcoat) on the inner walls of the flow channels of metallic or ceramic honeycomb bodies (monoliths).
Für die Abgasreinigung von Dieselmotoren sindFor the exhaust gas purification of diesel engines are
Beschichtungsmengen von 50 bis 300 g/l Volumen des Wabenkörpers vorteilhaft. Die notwendigenCoating amounts of 50 to 300 g / l volume of the honeycomb body advantageous. The necessary
Beschichtungstechniken sind dem Fachmann bekannt. So wird zum Beispiel die katalytische Zusammensetzung zu einer wässrigen Beschichtungsdispersion verarbeitet. Dieser Dispersion kann als Binder zum Beispiel Silicasol zugegeben werden. Die Viskosität der Dispersion kann durch geeignete Zusatzstoffe eingestellt werden, so dass es möglich ist, die benötigte Beschichtungsmenge in einem einzigen Arbeitsgang auf die Wandungen der Strömungskanäle aufzubringen. Ist dies nicht möglich, so kann die Beschichtung mehrfach wiederholt werden, wobei die frisch aufgebrachte Beschichtung jeweils durch eine Zwischentrocknung fixiert wird. Die fertige Beschichtung wird dann bei erhöhter Temperatur getrocknet und für die Dauer von 1 bis 4 Stunden bei Temperaturen von 300 0C bis 600 0C kalziniert .Coating techniques are known to the person skilled in the art. For example, the catalytic composition is processed into an aqueous coating dispersion. This dispersion may be added as a binder, for example, silica sol. The viscosity of the dispersion can be adjusted by suitable additives, so that it is possible, the required coating amount in a single operation on the Apply walls of the flow channels. If this is not possible, then the coating can be repeated several times, wherein the freshly applied coating is fixed in each case by an intermediate drying. The finished coating is then dried at elevated temperature and calcined for a period of 1 to 4 hours at temperatures of 300 0 C to 600 0 C.
Die Erfindung soll nun anhand einiger den Umfang der Erfindung nicht beschränkender Ausführungsbeispiele näher erläutert werden .The invention will now be explained in more detail with reference to some embodiments of the invention not limiting.
Ausführungsbeispiele :Exemplary embodiments:
Beispiel 1:Example 1:
Herstellung eines Gallo-Silikats (gemäß US 5,466,432):Preparation of a gallo-silicate (according to US 5,466,432):
Kolloidales Kieselgel (6,615 g, enthaltend 2,778 g SiO2) wird mit 1,723 g Tetrapropylammoniumbromid (TPABr), 0,45 g GaCl3- Lösung (enthält 0,067 g Gallium) und 3,238 gColloidal silica gel (6.615 g, containing 2.778 g of SiO 2 ) is charged with 1.723 g of tetrapropylammonium bromide (TPABr), 0.45 g of GaCl 3 solution (containing 0.067 g of gallium) and 3.238 g
Hexamethylentetramin (HMT) in 25 g Wasser unter Rühren 94 Min. homogenisiert. Die Reaktionsmischung mit den molaren Verhältnissen H2O/SiO2 = 30, SiO2/Ga2O3 = 92, HMT/SiO2 = 0,5, TPABr/SiO2 = 0,14 wird in einen mit Teflon ausgekleideten Autoklaven überführt, der eine Kapazität von 50 ml aufweist und bei 453 Kelvin für vier Tage und dem dabei entstehendem Druck umgesetzt. Nach Filtration und Waschen mit Wasser werden etwa 2 g eines kristallinen Gallosilikats erhalten. Anschließend wird das Gallosilikat bei Temperaturen oberhalb von 400 0C thermisch behandelt, um das organische Templat zu entfernen. Dabei wird mit Temperaturprogrammierter Ammoniumdesorption kontrolliert, dass keine Degalliierung erfolgt . Anschließend erfolgt eine wässrige Imprägnierung mit Platin. Das Gallosilikat wird anschließend getrocknet und bei Temperaturen oberhalb von 600 0C (650 bis 700 0C) kalziniert. Dies führt zu einer vollständigen Entfernung des Galliums aus dem Gitter. Anschließend erfolgt noch eine Reduktion mit Wasserstoff, um das sich gebildete, edelmetallhaltige Silikat zu aktivieren. Die Platinbeladung beträgt 2 %, bezogen auf das Gesamtgewicht des Silikats .Hexamethylenetetramine (HMT) in 25 g of water with stirring for 94 min. Homogenized. The reaction mixture with the molar ratios H 2 O / SiO 2 = 30, SiO 2 / Ga 2 O 3 = 92, HMT / SiO 2 = 0.5, TPABr / SiO 2 = 0.14 is transferred to a Teflon-lined autoclave which has a capacity of 50 ml and reacted at 453 Kelvin for four days and the resulting pressure. After filtration and washing with water, about 2 g of a crystalline gallosilicate are obtained. Subsequently, the gallosilicate is thermally treated at temperatures above 400 0 C to remove the organic template. It is controlled with temperature programmed ammonium desorption that no degalation occurs. This is followed by an aqueous impregnation with platinum. The gallosilicate is then dried and calcined at temperatures above 600 0 C (650 to 700 0 C). This leads to a complete removal of the gallium from the grid. Subsequently, a reduction with hydrogen takes place in order to activate the noble metal-containing silicate formed. The platinum loading is 2%, based on the total weight of the silicate.
Beispiel 2:Example 2:
Herstellung eines Gallo-Titan-Silikates (Ga-TS-I) :Preparation of a Gallo-titanium Silicate (Ga-TS-I):
In einem Rühr-Autoklaven werden 132,3 g Wasser, 233,6 g einer Tetrapropylammoniumhydroxidlösung (0,4 %) , 6 g Ga (NO3) 3.8H2O, 212,6 g Tetraethoxysilane (0,98% Si) und 7 g Tetraethyltitanate (0,95% Ti) gegeben. Danach wird der Autoklav verschlossen und über 12 h Ausheizzeit auf eine Temperatur von 140 0C gebracht und dort 71 h gehalten. Der Druck steigt dabei auf 21 bar. Das Produkt wird durch Zugabe von Flockungsmittel geflockt, abfiltriert, gewaschen und getrocknet. Danach wird in einer Serie mit IR-Spektroskopie festgestellt, dass bei 400 0C oder höher die Zersetzung des Tertaalkylammoniumions abgeschlossen ist (Fig. 1 Entfernung der Tetraalkylammoniumiomionen bei 4000C) und das Produkt wird dann entsprechend bei 4000C kalziniert.In a stirred autoclave, 132.3 g of water, 233.6 g of a tetrapropylammonium hydroxide solution (0.4%), 6 g of Ga (NO 3 ) 3 .8H 2 O, 212.6 g of tetraethoxysilane (0.98% Si) and 7 g of tetraethyl titanate (0.95% Ti). The autoclave is then sealed and placed for 12 hours heating time to a temperature of 140 0 C and held there for 71 h. The pressure rises to 21 bar. The product is flocculated by adding flocculant, filtered off, washed and dried. Thereafter, it is determined in a series with IR spectroscopy that at 400 0 C or higher, the decomposition of Tertaalkylammoniumions is completed (Fig. 1 removal of Tetraalkylammoniumiomionen at 400 0 C) and the product is then calcined at 400 0 C accordingly.
Ionenaustausch mit Pt (NH3) 4 (OH) 2-Lösung:Ion exchange with Pt (NH 3 ) 4 (OH) 2 solution:
Von dem eben hergestellten Ga-TS-I Zeolith wird eine Ammoniak- TPD (Temperatur-programmierte-Desorption) gemessen, (siehe Fig. 2) Es zeigt einen großen Peak für Brönsted-Acide Zentren (H+) an die NH3-gebunden ist und mit einem Peakmaximum bei 330 0C desorbiert. Eine Standardisierung der detektierten Ammoniakmenge über die gesamte Peakflache ergibt 314 μmol NH3/g Adsorption. Eine näherungsweise Auswertung des bei der höheren Temperatur liegenden Brönsted-Acidität-Peaks ergibt etwa 200 μmol H+. Es sollte daher gelingen ca. 200 μmol H+ gegen 100 μmol Pt2+ auszutauschen.An ammonia TPD (temperature-programmed desorption) is measured from the Ga-TS-I zeolite just prepared (see Figure 2). It shows a large peak for Brönsted acid centers (H + ) to the NH 3 -bonded is and with a peak maximum at 330 0 C desorbed. Standardization of the detected amount of ammonia over the entire peak area results in 314 μmol NH 3 / g adsorption. An approximate evaluation of the higher temperature Brönsted acidity peak gives about 200 μmol H + . It should therefore be possible to exchange about 200 μmol H + for 100 μmol Pt 2+ .
Daher werden 35 g des so hergestellten Ga-TS-I-Pulvers in 350 ml Wasser suspendiert. Zu dieser Suspension gibt man 4,25 g Pt (NH3) 4 (OH) 2-Lösung (16,04 %) und lässt 18 h Rühren. Es wird filtriert und getrocknet. Das Pulver wird im Ofen 3 h bei 550 0C kalziniert.Therefore, 35 g of the Ga-TS-I powder thus prepared is suspended in 350 ml of water. To this suspension is added 4.25 g of Pt (NH 3 ) 4 (OH) 2 solution (16.04%) and allowed to stir for 18 hours. It is filtered and dried. The powder is calcined in the oven for 3 h at 550 0C.
Das Produkt enthält 2,2% Platin.The product contains 2.2% platinum.
Fig. 3 zeigt ein IR-Spektrum des Produktes nach Beladung mit Kohlenmonoxid bei 77 K, das langsam mit He gespült wird. Es sind die CO-Schwingungen für CO an SiOH (2156 cm"1) und für Si- Ga bei 2171 cm"1 zu sehen. Es ist klar zu erkennen, dass nach einer Kalzinierung bei 550 0C noch viele Ga-Ionen im Zeolith vorhanden sind, die noch Azidität im Zeolith belassen.Fig. 3 shows an IR spectrum of the product after loading with carbon monoxide at 77 K, which is slowly rinsed with He. The CO oscillations for CO on SiOH (2156 cm -1 ) and for Si-Ga at 2171 cm -1 can be seen. It can be clearly seen that after calcination at 550 ° C., there are still many Ga ions in the zeolite which still leave acidity in the zeolite.
Fig. 4 zeigt im oberen IR-Spektrum unter CO bei 20 mbar ein Signal bei 2088 cm"1, das CO absorbiert an Pt (0) -Cluster zugeordnet wird. Die Frage, ob sich diese im Zeolith befinden, kann durch Zugabe eines starken sperrigen Liganden gelöst werden. Adamantannitril ist so groß, dass es nicht in die Zeolithporen gelangt. Eine Adsorption von Adamantannitril vor der CO-Zugabe sollte also die CO-Adsorption auf großen Clustern außerhalb des Zeolithen stark beeinträchtigen.Fig. 4 shows in the upper IR spectrum under CO at 20 mbar a signal at 2088 cm -1 which is associated with CO absorbed at Pt (0) cluster The question of whether these are present in the zeolite can be determined by adding a strong Adamantanenitrile is so large that it does not get into the zeolite pores, so adsorption of adamantanenitrile before CO addition should strongly affect CO adsorption on large clusters outside the zeolite.
Das untere Spektrum in Abb. 4 zeigt die CO-Adsorption nach Adamantannitril-Adsorption. Im Bereich von 2200-2300 cm"1 sind die Signale des adsorbierten Adamantannitrils zu erkennen. Aufgrund des sterischen Anspruchs haben auf den großen Clustern zwischen den Nitrilen einige CO-Moleküle Platz, die verbrückend zwischen 2 Pt-Atomen angeordnet sind. Diese zeigen eine geringe Absorption bei 1868 cm"1. Aus der Tatsache, dass der Hauptpeak jetzt bei 2073 cm'1, der ebenfalls CO auf Pt(O)- Clustern zuzuordnen ist, in seiner Intensität kaum geringer geworden ist, (Max. Adsorbance 0,85 gegen über 0,125), lässt sich folgern, dass ein erheblicher Teil der für die CO- Adsorption zur Verfügung stehenden Platinatome an der Oberfläche von Clustern in den Poren sitzt und nicht durch Adamantannitriladsorption blockiert wird.The lower spectrum in Fig. 4 shows the CO adsorption after adamantanenitrile adsorption. In the range of 2200-2300 cm "1 , the signals of the adsorbed adamantanenitrile can be recognized. Due to the steric demand, some CO molecules can be placed on the large clusters between the nitriles, bridging between 2 Pt atoms. These show a low absorption at 1868 cm -1 . From the fact that the main peak at 2073 cm '1 , which can also be assigned to CO on Pt (O) clusters, has hardly decreased in intensity (Max. Adsorbance 0.85 versus 0.125), it can be concluded that a significant portion of the platinum atoms available for CO adsorption sit at the surface of clusters in the pores and are not blocked by adamantanitrile adsorption.
Dieses Pt-Ga-TS-1-Material kann nun durch Kalzinieren variiert werden. Wenn eine hohe Kohlenwasserstoffadsorption des Zeolithen für eine KohlenwasserstoffSpeicherfunktion in einem DOC gewünscht ist, kann der Zeolith nach Kalzinieren bei 550 0C eingesetzt werden. Ist eine sehr gute CO-Oxidation gewünscht ist eine hohe Tendenz des Platins zu Pt(O) nötig. Hierfür muss dann durch Kalzinierung über 600 0C (ca. 700 0C) eine Wanderung des Galliums aus dem Gitter ausgelöst werden. Dadurch werden die sauren Zentren im Zeolith und die Reoxidationstendenz des Platins verringert, wodurch allerdings auch die Speicherungsfähigkeit für Kohlenwasserstoffe verringert wird.This Pt-Ga-TS-1 material can now be varied by calcination. If high hydrocarbon adsorption of the zeolite is desired for a hydrocarbon storage function in a DOC, the zeolite may be used after calcining at 550 ° C. If a very good CO oxidation is desired, a high tendency of the platinum to Pt (O) is necessary. Calcination above 600 ° C. (about 700 ° C.) requires a migration of the gallium from the lattice. As a result, the acid sites in the zeolite and the reoxidation tendency of the platinum are reduced, whereby, however, the storage capacity for hydrocarbons is reduced.
Fig. 5 zeigt ein TGA-DSC-Diagramm (Thermogravimetrische Analyse-Differential Scanning Kalorimetrie) des Ga-TS-I ohne Platin.Fig. 5 shows a TGA-DSC (Thermogravimetric Analysis Differential Scanning Calorimetry) diagram of Ga-TS-I without platinum.
Es ist klar zu sehen, dass oberhalb von 600 0C sehr wenig Masse verloren geht und ein leicht endothermes Signal der Wärmeaufnahme zu sehen ist. Hier wandert das Gallium aus dem Zeolith-Gitter . Ein kleiner Teil sublimiert weg, der größte Teil wandert an die Außenseiten des Zeolithen und verbleibt dort als Ga2O3.It can be clearly seen that above 600 ° C. very little mass is lost and a slightly endothermic signal of heat absorption can be seen. Here, the gallium migrates from the zeolite grid. A small part sublimes away, the largest Part migrates to the outer sides of the zeolite and remains there as Ga 2 O 3 .
Es gelingt mit dieser Methode Platin in eine Zeolithstruktur zu bringen, die in ihrer Struktur mehr als 1000 0C übersteht.It is possible with this method to bring platinum into a zeolite structure, which survives in their structure more than 1000 0 C.
Vergleichsbeispiel :Comparative Example
Titan-silikalit TS-I ist ein bekannter extrem thermostabiler Zeolith, dessen Struktur auch nach einer thermischen Behandlung oberhalb 1000 0C bestehen beleibt. Seine Herstellung ist z.B. in US 4,410,501 beschrieben.Titanium-silicalite TS-I is a well known extremely thermostable zeolite whose structure even after a thermal treatment above 1000 C 0 obese. Its preparation is described for example in US 4,410,501.
35 g dieses TS-I Pulvers werden in 350 mL Wasser suspendiert und gerührt. Zu dieser Suspension werden 4,25 g einer35 g of this TS-I powder are suspended in 350 ml of water and stirred. To this suspension are 4.25 g of a
Platintetraminhydroxidlösung (16.04 % Pt) zugegeben und über Nacht gerührt. Der Zeolith wird abfiltriert und getrocknet. Das Pulver wird auf Pt-Gehalt analysiert und enthält gemäß Analyse weniger als 0,2% Platin, was zeigt, dass ohne Brönstedt-saure Zentren kein Ionenaustausch gelingt. Platinum tetraminhydroxide solution (16.04% Pt) was added and stirred overnight. The zeolite is filtered off and dried. The powder is analyzed for Pt content and, according to analysis, contains less than 0.2% platinum, which shows that no ion exchange succeeds without Brönstedt acid sites.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von metallhaltigen kristallinen Silikaten, dadurch gekennzeichnet, dass ein Metall in ein Gallo-Silikat, Gallo-Titan-Silikat, Bor-Silikat oder Bor- Titan-Silikat eingebracht und anschließend das Gallo- Silikat, Gallo-Titan-Silikat, Bor-Silikat oder Bor-Titan- Silikat kalziniert wird.1. A process for the preparation of metal-containing crystalline silicates, characterized in that a metal is introduced into a gallo-silicate, gallo-titanium silicate, boron silicate or boron-titanium silicate and then the gallo-silicate, gallo-titanium silicate , Boron-silicate or boron-titanium silicate is calcined.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Metall in das Gallo-, Gallo-Titan- , Bor- oder Bor- Titan-Silikat über einen wässrigen Ionenaustausch, eine wässrige Imprägnierung, eine Incipient-Wetness-Methode oder einen Festkörperaustausch eingebracht wird.2. The method according to claim 1, characterized in that the metal is introduced into the gallium, gallium titanium, boron or boron titanium silicate via an aqueous ion exchange, an aqueous impregnation, an incipient wetness method or a solid-state exchange becomes.
3. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Metall in einer Menge von 0,1 bis 15 Gew.-% in das Gallo-Silikat, Gallo-Titan- Silikat, Bor-Silikat oder Bor-Titan-Silikat eingebracht wird.3. The method according to any one of the preceding claims, characterized in that the metal in an amount of 0.1 to 15 wt .-% in the gallo-silicate, gallo-titanium silicate, boron-silicate or boron-titanium silicate introduced becomes.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Metall ein Edelmetall oder Übergangsmetall ist, vorzugsweise ausgewählt aus der Gruppe bestehend aus Pt, Pd, Au, Ag, Rh, Re, Ir, Mn, Fe und/oder Cu.4. The method according to any one of the preceding claims, characterized in that the metal is a noble metal or transition metal, preferably selected from the group consisting of Pt, Pd, Au, Ag, Rh, Re, Ir, Mn, Fe and / or Cu.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Kalzinieren des Gallo- Silikats, Gallo-Titan-Silikats, Bor-Silikats oder Bor- Titan-Silikats bei Temperaturen oberhalb von etwa 500 0C erfolgt . 5. The method according to any one of the preceding claims, characterized in that the calcination of the gallo-silicate, gallo-titanium silicate, boron silicate or boron-titanium silicate takes place at temperatures above about 500 0 C.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass Gallium oder Bor aus dem Kristallgitter entfernt wird.6. The method according to claim 5, characterized in that gallium or boron is removed from the crystal lattice.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass nach dem Kalzinieren eine Reduktion mit Wasserstoff erfolgt.7. The method according to any one of the preceding claims, characterized in that after calcination, a reduction with hydrogen.
8. Metallhaltiges kristallines Silikat, dadurch gekennzeichnet, dass das Metall in dem Silikat im Wesentlichen in der Oxidationsstufe (0) vorliegt.8. Metal-containing crystalline silicate, characterized in that the metal is present in the silicate substantially in the oxidation state (0).
9. Metallhaltiges kristallines Silikat nach Anspruch 8, dadurch gekennzeichnet, dass das Silikat frei von Brönsted-aziden Zentren ist.9. Metal-containing crystalline silicate according to claim 8, characterized in that the silicate is free of Bronsted acid centers.
10. Metallhaltiges kristallines Silikat nach Anspruch 9, dadurch gekennzeichnet, dass das Silikat das Metall im Bereich von 0,1 bis 15 Gew.-% umfasst.10. The metal-containing crystalline silicate according to claim 9, characterized in that the silicate comprises the metal in the range of 0.1 to 15 wt .-%.
11. Metallhaltiges kristallines Silikat, hergestellt nach einem Verfahren nach einem der Ansprüche 1 bis 7.11. Metal-containing crystalline silicate, prepared by a process according to any one of claims 1 to 7.
12. Verwendung eines metallhaltigen kristallinen Silikats nach einem der Ansprüche 8 bis 11 als Hochtemperaturoxidationskatalysator oder als Dieseloxidationskatalysator .12. Use of a metal-containing crystalline silicate according to any one of claims 8 to 11 as a high-temperature oxidation catalyst or as a diesel oxidation catalyst.
13. Katalytische Zusammensetzung, dadurch gekennzeichnet, dass sie ein metallhaltiges kristallines Silikat nach einem der Ansprüche 8 bis 11 enthält.13. A catalytic composition, characterized in that it contains a metal-containing crystalline silicate according to any one of claims 8 to 11.
14. Katalytische Zusammensetzung nach Anspruch 13, dadurch gekennzeichnet, dass die katalytische Zusammensetzung das metallhaltige kristalline Silikat in einer Menge von 5 bis 70 Gew.-% enthält.14. A catalytic composition according to claim 13, characterized in that the catalytic composition is the containing metal-containing crystalline silicate in an amount of 5 to 70 wt .-%.
15. Katalytische Zusammensetzung, dadurch gekennzeichnet, dass weitere Metalloxide, Binder, Promotoren,15. Catalytic composition, characterized in that further metal oxides, binders, promoters,
Stabilisatoren und/oder Füllstoffe enthalten sind.Stabilizers and / or fillers are included.
16. Katalysatorformkörper, enthaltend ein metallhaltiges kristallines Silikat nach einem der Ansprüche 8 bis 11 oder eine katalytische Zusammensetzung nach einem der Ansprüche 13 bis 15.16. A shaped catalyst body comprising a metal-containing crystalline silicate according to any one of claims 8 to 11 or a catalytic composition according to any one of claims 13 to 15.
17. Katalysatorformkörper nach Anspruch 16, dadurch gekennzeichnet, dass das metallhaltige kristalline Silikat oder die katalytische Zusammensetzung als17. Catalyst molding according to claim 16, characterized in that the metal-containing crystalline silicate or the catalytic composition as
Beschichtung auf dem Katalysatorformkörper vorliegt. Coating is present on the catalyst molding.
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