EP2361154A1 - Silicates cristallins à teneur en métal - Google Patents

Silicates cristallins à teneur en métal

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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Withdrawn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)
English (en)
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/fr
Withdrawn legal-status Critical Current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

L'invention concerne de nouveaux silicates à teneur en métal, en particulier des silicates à activité redox ainsi que cristallins, un procédé de fabrication de silicates cristallins à teneur en métal ainsi que leur utilisation comme catalyseur d'oxydation haute température ou catalyseur d'oxydation diesel. L'invention concerne en outre une composition catalytique ainsi qu'un corps façonné de catalyseur, qui contient les silicates cristallins à teneur en métal.
EP09752302A 2008-11-13 2009-11-13 Silicates cristallins à teneur en métal Withdrawn EP2361154A1 (fr)

Applications Claiming Priority (2)

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DE102008057134A DE102008057134A1 (de) 2008-11-13 2008-11-13 Metallhaltige kristalline Silikate
PCT/EP2009/008104 WO2010054832A1 (fr) 2008-11-13 2009-11-13 Silicates cristallins à teneur en métal

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BR112014019483B1 (pt) * 2012-02-07 2021-04-20 Basf Se processo para a preparação de um material zeolítico
DE102012003032A1 (de) 2012-02-17 2013-08-22 Clariant Produkte (Deutschland) Gmbh Platin/Palladium-Zeolith-Katalysator
DE102013021750A1 (de) 2013-12-20 2015-06-25 Clariant International Ltd. Titanhaltige Zeolithkatalysatoren zur Oxidation von Methan in Abgasströmen
GB201401115D0 (en) 2014-01-23 2014-03-12 Johnson Matthey Plc Diesel oxidation catalyst and exhaust system
JP6235764B1 (ja) 2015-12-28 2017-11-22 トヨタ自動車株式会社 クラスター担持触媒及びその製造方法
JP6831292B2 (ja) * 2017-05-09 2021-02-17 トヨタ自動車株式会社 クラスター担持触媒及びその製造方法
EP3409358A1 (fr) 2017-06-01 2018-12-05 Paul Scherrer Institut Procédé de préparation d'un catalyseur pour l'oxydation du méthane, le catalyseur étant un catalyst métallique résistant au frittage supporté sur une zéolite contenant du métal alcalin
CN108285152B (zh) * 2018-02-23 2021-05-21 宝鸡文理学院 一种铜掺杂sba-15介孔分子筛材料的绿色高效合成方法
CN114247441B (zh) * 2021-11-23 2024-02-13 中海油天津化工研究设计院有限公司 均苯四甲酸酐加氢制1,2,4,5-环己烷四甲酸二酐的催化剂及其制备方法

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US9221038B2 (en) 2015-12-29
US20110274602A1 (en) 2011-11-10

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