Classifications

• • 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
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
  • B01J29/74—Noble metals
  • B01J29/7415—Zeolite Beta
• • 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
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/068—Noble metals
• • 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
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
  • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
  • B01J29/44—Noble metals
• • 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
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
  • B01J29/74—Noble metals
• • 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
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/393—Metal or metal oxide crystallite size
• • 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
  • B01J35/396—Distribution of the active metal ingredient
• • 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
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
• • 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
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • 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
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/617—500-1000 m2/g
• • 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
  • B01J37/0201—Impregnation
• • 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
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • 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
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/088—Decomposition of a metal salt
• • 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
  • B01D2255/10—Noble metals or compounds thereof
  • B01D2255/102—Platinum group metals
  • B01D2255/1023—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/50—Zeolites
  • B01D2255/502—Beta zeolites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/502—Carbon monoxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
  • B01D2257/702—Hydrocarbons
  • B01D2257/7022—Aliphatic hydrocarbons
• • 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
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
  • B01D53/864—Removing carbon monoxide or hydrocarbons
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/10—Infrared [IR]
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction

Definitions

• the present invention relates to a method for
• Catalyst as well as the use of the catalyst in the oxidation catalysis.
• Oxidation catalysts used in the exhaust air purification for the oxidation of mostly organic compounds Supported catalysts loaded with noble metal are used in the
• a carrier material is impregnated with a noble metal salt solution of the desired noble metal. After removal of the solvent from
• Support material in a subsequent step is then calcined in a further step, the support material, wherein the noble metal by the thermal treatment in a
• the oxide form already the catalytically active species, so that the catalyst can be used in this form. It is also possible to convert the noble metal oxide species in a further step, for example by means of hydrogen, carbon monoxide or wet chemical reducing agent in the highly dispersed noble metal of oxidation state 0, which can also act as a catalytically active species.
• the activity of supported noble metal catalysts is usually dependent on the size of the noble metal or. - oxide particles.
• the supported noble metal catalysts known in the prior art have the disadvantage that, in the course of their use, they are sintered due to sintering of the precious metal ⁇ or. oxide particles to larger units and a concomitant reduction in catalytically active surface of activity lose.
• the speed of this so-called thermal aging process is dependent on the height of the temperature at which the catalyst is used. In fact, as the feed temperature increases, the speed of the aging process increases, for which presumably an increased mobility of the noble metal /
• High temperature applications have high activity and are subject to only a small thermal aging process.
• Catalysts in which the noble metal is located primarily in the pores of zeolites This results in a very high activity and aging stability of the catalyst. adversely is the need for high quenching temperatures above 700 ° C to decompose the Su1fit precursor compounds used.
• Another disadvantage of these catalysts is also the low sulfur tolerance, which is further reduced by the use of the sulfite precursor compounds.
• the known in the art especially platinum-containing catalysts with respect to the oxidation of alkanes too low activity. The object of the present invention was therefore to provide a catalyst which in oxidation reactions, in particular in the oxidation of alkanes, a high activity and a high aging and
• protective gases are gases or gas mixtures which are used as inert protective atmosphere and to avoid unwanted chemical
• Reactions can be used, for example, to keep oxygen and / or hydrogen away from sensitive substances.
• protective gases noble gases, e.g. Argon, helium, neon or nitrogen used.
• the substantially uniform coverage of the zeolite with the Pt and Pd precursor compounds forms the basis for the fact that in the subsequent calcination step, which leads to the decomposition of the Pt and Pd precursor compounds, or at
• the impregnation of the zeolitic carrier material can be carried out by all methods known to the person skilled in the art. Particularly preferably, the impregnation of the
• the Pt and Pd precursor compound can be, for example, nitrates, acetates, oxalates, tartrates, formates, amines, sulfides, carbonates, halides or hydroxides of the corresponding noble metals, where nitrates
• the precursor compounds are intended to be present in the Be substantially sulfur-free. It may also be preferred for the purposes of the invention that the Pt and the Pd precursor compounds have the same anion, for example
• Drying of the impregnated zeolitic carrier material is preferably carried out below the decomposition point of the Pt TM and Pd precursor compound. Drying preferably takes place in air. Drying temperatures are usually in the range of 50 to 150 ° C, preferably 80 to 120 ° C.
• the calcining is preferably carried out at temperatures of 300 to 600 ° C, more preferably at 400 to 550 ° C.
• the calcination time is preferably 1 to 8 hours, more preferably 2 to 6 hours and especially about 3-5 hours.
• the method comprises the further steps of: d) producing a washcoat of the impregnated and calcined zeolitic carrier material, e) coating a carrier body with the washcoat, f) drying and calcining the coated carrier body in air.
• a zeolitic carrier material or a zeolite material is used as carrier material for the impregnation steps. These two terms are used synonymously in the context of the invention.
• zeolite material according to a definition of International
• Mineralogical Association (DS Coombs et al., Can. Mineralogist, 35, 1997, 1571) understood a crystalline substance having a structure characterized by a skeleton of interconnected tetrahedra. Each tetrahedron consists of four oxygen atoms surrounding a central atom, the framework containing open cavities in the form of channels and cages, normally occupied by water molecules and extra framework cations which can be exchanged. The channels of the material are large enough to allow guest connections access.
• dehydration usually occurs at temperatures below about 400 ° C and is for the most part reversible.
• the abovementioned zeolite material is preferably a microporous or a mesoporous one
• Zeolite material is. It should be under the terms
• Zeolite material "according to the classification of porous solids according to IUPAC (International Union of Research and Applied Chemistry) zeolite materials are understood, the pores of a
• Diameter of less than 2 nm resp. have a diameter of 2 nm to 50 nm.
• Zeolite material may preferably correspond to one of the following structural types: ABW, ACQ, AEI, AEL, AEN, AET, AFG,
• GIU GIU
• GME GON
• GOO GOO
• HEU HEU
• IFR IHW
• ISV ISV
• ITE ITH
• ITW ITW
• IWR IWR
• MCM mesoporous silicates which are known as MCM -41 or MCM-48 MCM-48 has a 3D structure
• MCM-41 Mesopores, whereby the catalytically active metal in the pores is particularly easily accessible.
• MCM-41 is most preferred and has a hexagonal array of mesopores of uniform size.
• the MCM-41 zeolite material has a SiO 2 / Al 2 O 3 M0 ratio of preferably greater than 100, more preferably greater than 200, and most preferably greater than 300.
• Zeolite materials which can be used in the present invention are those which are referred to in the literature as MCM-1, MCM-2, MCM-3, MCM-4, MCM-5, MCM-9, MCM-10, MCM- 14, MCM-22, MCM-35, MCM-37, MCM-49, MCM-58, MCM-61, MCM-65 or MCM-68.
• Which zeolitic carrier material or zeolite material is to be used in the method according to the invention depends primarily on the intended use of the method according to the invention
• the type of structure the pore diameter, the channel diameter, the chemical composition, the
• Ion exchange ability as well as activation properties tailor-made for a specific purpose.
• zeolite material may be a silicate
• Aluminum silicates and titanium silicates are particularly preferred.
• aluminosilicate as defined by the International Mineralogical Association (D.S. Coombs et al., Can. Mineralogist, 35, 1997, 1571) discloses a crystalline
• zeolite materials can be used in the context of the present invention both in the alkali form,
• zeolite material in a mixed form, for example in an alkali / alkaline earth mixed form.
• Another object of the invention is a catalyst which has been prepared by the process according to the invention, wherein the catalyst is a bimetallic catalytically active
• Composition containing Pt and Pd on a zeolite carrier material Composition containing Pt and Pd on a zeolite carrier material.
• Composition that is loaded with precious metal zeolitic material, a BET surface area of more than 400 m / g.
• the bimetallic catalytically active composition preferably has a Pt content of 0.2 to 1.5 wt. -%, Based on the catalytically active composition.
• Composition preferably has a Pd content of 0, 8 to 4, 0 wt. -%, Based on the catalytically active composition.
• the catalytically active composition can preferably be processed with a preferably silicate binder to a washcoat and as Washcoat coating on a Carrier body are applied.
• the mass ratio binder / catalytically active composition is in this case 0.05-0.5, preferably 0.1-0.3 and particularly preferably 0, 15-0, 25, based in each case on the solids content of binder and catalytically active composition.
• the catalytically active composition may also be formed as a full catalyst, for example as an extrudate of a noble metal-coated zeolite.
• the catalyst in the form of a coating catalyst or a full catalyst also has 0, 5 to 3, 0 wt. -% Pt, preferably 0.15 to 1.45 wt. -% Pt and 1 to 5 wt. -% Pt, preferably 0, 6 to 3, 8 wt. -% Pd relative to the
• the Pd / Pt weight ratio in the bimetallic catalytically active composition or in the washcoat coating is preferably in the range of 6: 1 to 1: 1, and more preferably about 4: 1 to 2: 1.
• the Pt and Pd are located essentially in the pores of the zeolitic carrier material.
• Pt and Pd are preferably present in aggregates of ⁇ 5 nm.
• the precious metal aggregate size / cluster size is essentially determined by the size of the pore intersections.
• the BEA zeolite with a three-dimensional system of pores of max. 7.7 angstroms (0.77 nm) is the diameter of one
• the invention furthermore relates to the use of the catalyst described above as oxidation catalyst, in particular as catalyst for the oxidation of alkanes, for example ethane, methane, propane, etc. but also from
• Olefins and solvent vapors Olefins and solvent vapors.
• FIG. 1 shows the XRD spectrum of an invention
• FIGS. 4a, 4b performance data in the oxidation of
• FIGS. 5a, 5b Performance data in the oxidation
• FIGS. 6a, 6b performance data in the oxidation of
• FIG. 7 Performance comparison according to the invention vs.
• the catalysts of the invention were prepared in a 2-step process.
• a BEA150 zeolite was treated with a solution of platinum nitrate and palladium nitrate by means of Incipient Wetness technology, and the charged zeolite was then dried in air at 90 ° C. for 16 h and then at 550 ° C. under argon for 5 h calcined.
• a BEA150 zeolite was applied in an analogous manner with platinum and palladium nitrate by means of "Incipient Wetness" technology applied at 90 ° C and then calcined at 550 ° C under air for 5 h.
• Table 1 summarizes the properties of the zeolite samples prepared in the course of the investigations (formulation according to the invention and comparative example 1).
• the calcined PtPd zeolite according to the invention and that of Comparative Example 1 were treated with bindzil (binder material) and water to form a washcoat, and this washcoat was then coated on corderite honeycombs.
• the coated Corderitwaben were blown out with compressed air, then dried overnight at 150 ° C under air and finally calcined at 550 ° C for 3 h.
• FIG. 1 shows the XRD spectrum of a PtPd-BEA150 zeolite according to the invention prepared according to the above specification, and that of the comparative formulation. Both samples have no reflections for metallic Pt and Pd. The signals for noble metal oxides are barely detectable. All major reflexes contain almost exclusively signal components of the BEA150 zeolites. It can be concluded from this that both Pt and Pd are present in favor of the performance of highly dispersed form. The missing of
• FIGS. 2 and 3 show the IR spectra of the PtPd-BEA150 zeolite according to the invention and of the
• Comparative Example 1 after CO chemisorption without and with addition of adamantanecarbonitrile The measurement of IR spectra after CO chemisorption is a widely used technique for studying the nature and dispersion of noble metal species in noble metal-containing catalysts. CO can reach and interact with noble metal species both inside and outside the pores, generating signals that can be evaluated by IR spectroscopy.
• Nitriles such as adamantanecarbonitrile, interact more strongly with noble metal species and are therefore preferentially adsorbed by them. Therefore, it is possible to sequester noble metal species for CO chemisorption using nitriles.
• Nitrile molecules with diameters equal to or greater than the pores of the zeolites can not penetrate into zeolite pores and thus selectively mask noble metal species outside the pores.
• Adamantanecarbonitrile has a molecular diameter> 0, 6 nm. This is comparable to the diameters of the pore openings of the BEA zeolite (0.56-0.7 nm), so that adamantanecarbonitrile can be used to selectively remove noble metal species outside the zeolite pores.
• adamantane carbonitrile vapor was metered onto the samples to sequester the noble metal species outside the zeolite pores, followed by further pressurization with 20 mbar CO. Then the second IR spectrum was recorded. The difference in both IR spectra shows those noble metal species that are outside of the zeolite pores and therefore can be masked by adamantane carbonitrile vapor. All spectra themselves were recorded using a Thermo 4700 FTIR spectrometer with a resolution of 4 cm -1 .
• FIG. 2 shows the IR spectra of the CO chemisorption of the Pt-Pd-BEA150 zeolite according to the invention
• Comparative Example 1 Furthermore, in Comparative Example 1 at 1900 cnT 1 there is an almost completely maskable absorption band by addition of adamantanecarbonitrile, which is not present in the Pt-Pd-BEA150 zeolite according to the invention. Also, for higher loaded ("overloaded") PtPd - BEA150 / Ar zeolites, the 1900 cm _i ⁇ band may occur, for example at 1.13% Pt and 3.4% Pd, but not at 0.92% Pt / 2 , 8% Pd. First material, however, shows a significantly lower performance in the alkane oxidation ion.
• Table 2 shows the catalyst patterns prepared therefrom (including comparative samples).
• Figures 4a-c and 5a, 5b summarize the performance data obtained, measured in the simultaneous oxidation of 800 ppmv CO, 1000 ppmv methane, 360 ppmv ethane, 200 ppmv ethylene and 180 ppmv propane in a carrier gas consisting of 10% oxygen and 3% water in nitrogen. The measurements were carried out at a GHSV of 40,000 IT first Subsequently, the catalyst patterns were still in the Oxidat ion of 200 ppmv ethyl acetate in air at a GHSV of 40000 IT 1 tested.
• the aging was carried out with the samples of the freshness tests, these were treated for 24 h at 650 ° C in a muffle furnace and then retested.
• For the sulfurization fresh samples were exposed to a mixture of 100 ppm SO 2 , 250 ppm C 3 H 8 and 5% H 2 O in air at 500 ° C for 125 h.
• the loss of activity of the EnviCat 50300 is typically about 60-75% in the alkane oxidation ion under these conditions.
• BEA150 honeycombs with comparable precious metal content (BEEZ 00387-2) and with significantly lower noble metal content (BEEZ 00812-1) compared to the comparative examples.

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  • 2013-02-18 CN CN201380009819.8A patent/CN104220163B/zh not_active Expired - Fee Related
  • 2013-02-18 BR BR112014020236A patent/BR112014020236A8/pt active Search and Examination
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