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WO2011018219A2 - Corps moulé à action thermo-catalytique, procédé permettant sa réalisation et son utilisation - Google Patents

Corps moulé à action thermo-catalytique, procédé permettant sa réalisation et son utilisation Download PDF

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Publication number
WO2011018219A2
WO2011018219A2 PCT/EP2010/004928 EP2010004928W WO2011018219A2 WO 2011018219 A2 WO2011018219 A2 WO 2011018219A2 EP 2010004928 W EP2010004928 W EP 2010004928W WO 2011018219 A2 WO2011018219 A2 WO 2011018219A2
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WO
WIPO (PCT)
Prior art keywords
lithium
molding according
thermocatalytically
shaped body
thermocatalytically active
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.)
Ceased
Application number
PCT/EP2010/004928
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German (de)
English (en)
Other versions
WO2011018219A3 (fr
Inventor
Inka Henze
Matthias Bockmeyer
Andrea Anton
Gerhard Weber
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Schott AG
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Schott AG
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Publication of WO2011018219A2 publication Critical patent/WO2011018219A2/fr
Publication of WO2011018219A3 publication Critical patent/WO2011018219A3/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • 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
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B01D2255/2025—Lithium
    • 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
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9202—Linear dimensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9207—Specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • 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
    • 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
    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a thermocatalytically active molding, to a process for its preparation and to its use.
  • the catalytic activity of lithium has been known for a long time, for example for the catalysis of chemical reactions, such as polymerization reactions, alcohol hydrogenations and hydrogenations.
  • GB 834217 describes a Ziegler-Natta catalyst consisting of a titanium compound which has preferably been treated with an aluminum compound and in one example also with lithium aluminum hydride. This catalyst is used to catalyze the polymerization reaction of polyolefins from solution.
  • No. 5,227,530 B1 describes a multimetal oxide catalyst of crystalline copper / chromium / aluminum / borate for converting alcohol into aldehydes and ketones. Among others, lithium is used as metallic doping.
  • DE 37 37 277 C2 describes a heterogeneous catalyst based on reduced copper / zinc oxides, which in addition to nickel and cobalt still contain additives of alkali metals. The additives cause a higher selectivity of the reaction and thus fewer by-products.
  • thermocatalytically active layers and surfaces are well known and are used for the decomposition of pollutants, such as in the stationary or mobile exhaust gas purification or to support the self-cleaning of organic contaminants, such as in ovens.
  • pollutants such as in the stationary or mobile exhaust gas purification or to support the self-cleaning of organic contaminants, such as in ovens.
  • these are precious metal coatings, eg platinum coatings, as described in DE 101 50 825 to enamel coatings containing transition metals.
  • thermocatalytic purification In a thermocatalytic purification, the decomposition and oxidation or the combustion of pollutants and gaseous exhaust gases takes place by means of catalytically or oxidatively acting agent even at reduced temperatures, ie temperatures well below 500 0 C. Therefore, from a cost standpoint, catalytic systems are also known Pyrolysis systems preferable. In catalytically active cleaning systems, the surface to be cleaned is usually provided with a thermocatalytic active coating.
  • the document US Pat. No. 7,297,656 B2 describes catalytic layers which degrade diesel soot.
  • the coating consists of doped Metallloxidplatinaten, wherein in addition to platinum and lithium may be included.
  • a catalyst is described from a combination of lithium and platinum or palladium.
  • the lithium should prevent poisoning reactions of platinum or palladium.
  • Lithium is produced in an Al 2 O 3 support in the strongest possible bond, to which then the catalytically active components platinum or palladium and other metals are applied. This type of catalyst is used for emission control.
  • a method for reducing the ignition temperature of diesel soot filtered out of exhaust gas from diesel engines, in which the exhaust gas is passed over a catalytically active substance which is applied to a cordierite monolithic filter body, is known from document EP 0 105 113 B1.
  • the catalytically active substance is Li 2 O, CuCl 1 V 2 O 5 with 1 to 30 wt .-% alkali metal oxide, vanadate, preferably of Li, Na, K or Ce, or perrhenate, preferably of K or Ag.
  • the object is achieved by a thermocatalytically active molding, wherein the molding consists of at least two components mixed together, wherein at least one of the components consists of at least one lithium compound or contains at least one lithium compound and, if a lithium compound Li 2 ⁇ , at least another lithium compound, which is not in the form of Li 2 O, is present.
  • thermocatalysis or thermocatalytic means here that the activation energy of a reaction is reduced by means of the molding according to the invention such that the reaction temperature is lowered.
  • the lithium compound is essentially the thermocatalytically active part of the component.
  • the shaped body can be free of Li 2 O, except for unavoidable impurities, such as occur, for example, in the raw materials used or are formed as a result of the production.
  • the component consisting of the lithium compound or containing the lithium compound may contain at least 2% by weight, preferably at least 3% by weight and more preferably at least 5% by weight of lithium.
  • the component consisting of the lithium compound or containing the lithium compound may have a cation ratio of lithium to other cations of the component. greater than 1: 15, preferably greater than 1:10, particularly preferably greater than 1: 5.
  • the shaped body may contain, in addition to the lithium compound, other thermocatalytically active compounds.
  • the shaped body can not contain any further thermocatalytically active compounds.
  • the shaped body is preferably suitable for thermocatalysis of reaction at temperatures below 400 ° C., preferably below 380 ° C., and more preferably below 350 ° C.
  • the lithium compound may be an amorphous inorganic and / or a crystalline inorganic compound, in particular a single and / or multi-component compound of the oxides and / or nitrides and / or carbides and / or fluorides of Si, B, Ge, Bi, Al, Na , Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm , Ta, W be.
  • the lithium compound may be in the form of mixed oxides, ceramics, glass ceramics or glasses.
  • the lithium compound may be an inorganic lithium salt, in particular lithium phosphate, lithium nitrate, lithium halide or lithium sulfate, a metal-organic lithium compounds, in particular lithium acetate, lithium citrate tetrahydrate, lithium propionate or a lithium derivative of carboxylic acids.
  • inorganic lithium salt in particular lithium phosphate, lithium nitrate, lithium halide or lithium sulfate
  • metal-organic lithium compounds in particular lithium acetate, lithium citrate tetrahydrate, lithium propionate or a lithium derivative of carboxylic acids.
  • At least one of the components may be a filler, a matrix material or a mixture of both.
  • the matrix material may contain at least one inorganic material selected from the group of glasses, glass solders or sol-gel matrices which are preferred Si, B, Ge, Bi 1 Al, Na, Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce Gd 1 include La, Sm, Ta, W 1.
  • the matrix material may also contain at least one organically based compound selected from the group of waxes, polymers, surfactants, carboxylic and fatty acids, oils, resins, silicone resins, or mixtures thereof.
  • the shaped body can have fillers into which lithium is introduced and which are themselves thermocatalytically active.
  • the shaped body can have particulate fillers, in particular round, platelet-shaped or irregularly shaped particles, granules, spheres or hollow spheres, fibers, in particular fibrous tissue, short fibers, hollow fibers, whiskers or nanotubes.
  • particulate fillers in particular round, platelet-shaped or irregularly shaped particles, granules, spheres or hollow spheres, fibers, in particular fibrous tissue, short fibers, hollow fibers, whiskers or nanotubes.
  • the shaped body may have at least one further property, in particular an optical reflection in the infrared, visible and / or ultraviolet range of the light, a filter for defined wavelengths of light, a color, a thermal conductivity and / or a biocidivity.
  • the molded article may have a total porosity ranging from 2 to 90% by volume, preferably from 5 to 70% by volume, and more preferably from 25 to 60% by volume.
  • the shaped body may have micropores with an average pore diameter of less than 2 nm.
  • the shaped body may have meso- and macropores, which are preferably formed by air bubbles and / or by cavities resulting from burnout of organically based compounds and fillers.
  • the molding may have an inner surface area of 15 to 3000 m 2 / g, preferably 50 to 1500 m 2 / g, and more preferably 250 to 1000 m 2 / g.
  • the inner surface is determined by the multi-point BET method.
  • the shaped body can have a hierarchical structure.
  • thermocatalytically active shaped article is characterized in that the shaped article is produced by providing a liquid to viscous or solid mass, shaping the composition, drying and baking.
  • thermocatalytically active shaped article is characterized in that the shaped article is produced by template process, extrusion process, melt process, sintering process, slip casting or foaming.
  • a process which uses powdery starting products which are used as dry powders or modified by means of a liquid organic and / or inorganic additive.
  • the molded article is used in or on combustion chambers, such as fireplaces, stoves, fireplace interior linings, cladding of chimney exhaust pipes, filters for fireplaces, industrial ovens; in heating systems, lining of exhaust pipes, filters for exhaust pipes; in or on cooking, roasting, baking and grilling devices, interior linings, exhaust ducts, exhaust duct filters, fryers, microwaves, on or in extractor hoods; in or on reactors, such as chemical reactors or Raffeerien series; in or at incineration plants, in particular in waste incineration plants, energy plants or crematoria; in or on automobile exhaust systems, in particular diesel soot filters, Oxidation catalysts, cladding in exhaust systems, such as exhaust pipes.
  • combustion chambers such as fireplaces, stoves, fireplace interior linings, cladding of chimney exhaust pipes, filters for fireplaces, industrial ovens; in heating systems, lining of exhaust pipes, filters for exhaust pipes; in or on cooking, roasting, baking and grilling devices, interior linings, exhaust ducts,
  • thermocatalytically active form body it is N & N longer therefore possible reactions at temperatures less than 400 0 C, preferably less than 38O 0 C, more preferably less than or equal 35O 0 carry C with a sufficient rate of degradation that would otherwise occur at higher temperatures ,
  • the molding preferably has a high surface area and is inexpensive to obtain.
  • lithium compounds are used which are not hygroscopic, behave neutrally with respect to other components and do not corrosively attack these components.
  • those lithium compounds are suitable which have a pH of ⁇ 11 in aqueous solution.
  • the pH refers to the values given in safety data sheets of Merck Chemicals (Merck KGaA, Darmstadt, Germany) and is generally based on 50 g / L of water at 20 ° C. If the solubility of the substances is too low, the pH values are also given for smaller amounts, such as, for example, 5 g / l water or higher temperatures.
  • thermocatalytically active molding according to the invention preferably has at least partially a thermocatalytically active surface, at which a catalytic combustion of carbon black and other organic or oxidizable compounds at temperatures below 400 ° C, preferably less than 380 0 C, more preferably less than or equal to 350 0 C can be achieved.
  • thermocatalytically active component by using moldings comprising at least one lithium compound as the thermocatalytically active component, the temperature at which a catalytic organic decomposition reaction such as e.g. the soot combustion, or takes place in the self-cleaning property of food contamination, can be significantly reduced and takes place even at temperatures less than or equal to 350 ° C.
  • a catalytic effect on the oxidation of carbon monoxide and short-chain hydrocarbons, as well as a reduction of nitrogen oxides in the exhaust gas flow was demonstrated.
  • the molding may furthermore have at least one thermocatalytically active component, this component comprising lithium in at least greater than or equal to 2% by weight, preferably greater than or equal to 3% by weight, especially greater than or equal to 5% by weight, based on the Contains cation ratio.
  • the term shaped body as used herein includes all three-dimensional shapes.
  • the molded body can be configured differently. It may also be in the form of, for example, flat or three-dimensionally shaped plates, porous filters, fiber mats, fiber composites, fiber bundles, fiber fabrics, fiber felts, nonwoven fabrics, open pore solids and / or closed pores, granules, sintered ceramics, glass ceramics, optoceramics, molded articles in particulate form, for example in loose or pressed powder form such as particles, nanotupes, whiskers and / or short fibers.
  • the molded article is not subject to any limitation in terms of shape in the invention, so that flat, round, rounded, large and small shapes can be used.
  • the lithium is present, for example, in an amorphous and / or crystalline material.
  • inorganic amorphous components of this material for example, single and / or multi-component systems of oxides and / or nitrides and / or carbides and / or fluorides of Si, B, Ge, Bi, Al, Na, Li, K, P, Mg , Ca, Sr, Ba, Mn, Ni, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm.
  • inorganic crystalline components for example, single and / or multi-component systems of oxides and / or nitrides and / or carbides and / or fluorides of Si, Li, B, Ge, Bi, Al, Na, K, P, Mg, Ca , Sr, Ba, Mn, Ni, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm.
  • the lithium of the active component can be present in the form of reacted oxides, mixed oxides, ceramics or glassy mixtures.
  • thermocatalytically active component Characteristic of such a special embodiment of a thermocatalytically active component is that the element ratio of lithium as a thermocatalytically active element to other cations of the thermocatalytically active component is greater than 1:15, preferably greater than 1:10, particularly preferably greater than 1: 5 lies.
  • organic residues and / or decomposition products of organic functional groups such as epoxy, methacrylate, allyl, vinyl, methoxy, ethoxy, propylate, butylate, acetate, propionate can also be present in the thermocatalytically active component -, formate, methyl, ethyl or phenyl groups.
  • Temperature stable functional groups such as methyl or phenyl groups may be attached to a transition metal oxide or metal oxide.
  • the lithium is in the thermocatalytically active component of the molding, for example, also completely or partially in one Polysiloxane, such as a temperature-stable methyl and or phenyl-functionalized linear and / or branched polysiloxane before.
  • Polysiloxane such as a temperature-stable methyl and or phenyl-functionalized linear and / or branched polysiloxane before.
  • lithium compounds are present in the molded body, preferably in a binding matrix.
  • the term lithium compound as used herein includes all ionic compounds having a pH ⁇ 11 which have at least one lithium ion.
  • organic lithium-containing compounds are also included, such as lithium acetate, lithium citrate tetrahydrate, lithium propionate and lithium derivatives of the carboxylic acids, as well as mixed oxides containing lithium and all lithium ions contained compounds, eg arise during a thermal decomposition of lithium organyls or by the reactive reaction of metallic lithium.
  • thermocatalytically active component or / and the thermocatalytically active molded body can consist of a zeolite in which the thermocatalytically active lithium can be introduced, for example, as an active metal ion via an ion exchange in the zeolite.
  • the thermocatalytically active molding may consist of one or more fillers, or a matrix, or mixtures thereof.
  • the shaped body contains at least one component which contains at least greater than or equal to 2% by weight of thermocatalytically active lithium ions and is thermocatalytically active.
  • either the filler (s) and / or the matrix may comprise or consist entirely of the thermocatalytically active component according to the invention.
  • the fillers have a three-dimensional shape. These may, for example, take the form of particles, such as round, platelet-shaped or irregularly shaped particles, granules, spheres or hollow spheres, the form of fibers, such as fibrous tissue, short fiber, hollow fibers, Whisker or Nanotubes.
  • the molding may have one or more fillers of different shapes, sizes and composition.
  • the mean primary particle size of the material constituting the active component of the material is between 0.1 nm and 1 mm, preferably between 1 nm and 100 ⁇ m, particularly preferably between 10 nm and 10 ⁇ m.
  • the average agglomerate size of the material constituting the active component of the material is between 0.1 nm and 10 mm, preferably between 10 nm and 1000 ⁇ m.
  • the average fiber diameter of a thermocatalytically active component is 1 .mu.m to 1 mm, preferably 6 .mu.m to 100 .mu.m.
  • a preferred embodiment is to use fillers of inorganic amorphous and / or crystalline materials.
  • these filler materials for example, single and / or multi-component systems of oxides and / or nitrides and / or carbides and / or fluorides of Si, B, Ge, Bi, Al, Na, Li, K, P, Mg , Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W.
  • inorganic crystalline filler materials for example, single and / or multi-component systems of oxides and / or nitrides and / or carbides and / or fluorides of Si, B, Ge, Bi, Al, Na, Li, K, P, Mg, Ca , Sr, Ba, Mn, Ni, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm.
  • the fillers according to the invention may contain lithium as thermocatalytically active component, or be catalytically inactive, or contain other known catalytically active ingredients.
  • the fillers are still organic radicals and / or decomposition products of organic functional
  • Groups such as epoxy, methacrylate, AlIIyI, vinyl, methoxy, ethoxy, propylate, butylate, acetate, propionate, formate, methyl, ethyl or phenyl groups may be included.
  • Temperature stable functional groups such as methyl or phenyl groups may be attached to a transition metal oxide or metal oxide.
  • the filler material consists entirely or partially of a polysiloxane, such as a temperature-stable methyl- and / or phenyl-functionalized linear and / or branched polysiloxane.
  • thermocatalytically active noble metals such as Pt, Rh, Pd, Ru, Au, Ag can be contained in the molding. These can be added in small amounts for doping, to lower the light-off temperature even further, or to increase the reactive activity.
  • Dopants may also be doped with the above listed elements such as C, Si, B, Ge, Bi, Al, Na, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W take place. Dopings are preferably added in sizes of less than 2% by weight.
  • the surface of the fillers and / or the shaped body may be porous or non-porous structured.
  • the porosity is in the range of 2 to 90% by volume, preferably 5 to 70% by volume.
  • the fillers can be used for shaping, for adjusting the viscosity, or for other functionalities.
  • the mixture it is possible for the mixture to have fillers with functional properties, such as optical reflection, e.g. in the infrared or ultraviolet range, filters at defined wavelengths, or color, or thermal conductivity, or to add fillers having a biocidal effect.
  • Fillers as described in the text, may be at least partially surrounded by a matrix.
  • the shaped body can also be constructed only from a matrix and contain no fillers.
  • a binding matrix may consist of both an inorganic and an organic matrix or mixtures thereof.
  • the shaped body comprises the thermocatalytic component according to the invention and a binding matrix with a lithium compound.
  • An inorganic matrix is understood to mean the following compounds: glasses and glass solders, sol-gel matrices. These inorganic matrices preferably contain elements such as Si, B, Ge, Bi, Al, Na, Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W.
  • elements such as Si, B, Ge, Bi, Al, Na, Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W.
  • an inorganic sol-gel matrix is preferred.
  • the preparation of such sol-gel systems are known to the person skilled in the art.
  • such sol-gel systems are suitable which form a stable shaped body after drying or after annealing.
  • Particularly preferred are systems which lead in the overall system to a low shrinkage, preferably less than 60%, particularly preferably less than 40%.
  • the sol-gel matrix is dissolved in water, an organic solvent or an aqueous / organic solvent mixture, such as a mixture of water and at least one solvent selected from the group of alcohols, polyhydric alcohols, acetones, ketones, acetylacetone, ethyl acetate, 2 Butoxy-ethanol, 1-propanol, 2-propanol, methanol, ethanol and other solvents known in the art by acidic or basic catalyzed hydrolysis.
  • These sols are stable solutions having a solids content typically in the range of about 1 to about 40 weight percent.
  • the resulting sol-GeI systems preferably consist of a network of semimetal or metal oxides, such as oxides of the elements Si, B, Ge, Bi, Al, Na, Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni 1 Co 1 Cr, V, Sn, Zn 1 In, Fe, Ti 1 Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W or mixtures thereof.
  • semimetal or metal oxides such as oxides of the elements Si, B, Ge, Bi, Al, Na, Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni 1 Co 1 Cr, V, Sn, Zn 1 In, Fe, Ti 1 Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W or mixtures thereof.
  • an organic matrix is understood as meaning an organically based compound which may be composed of waxes, polymers, surfactants, carboxylic and fatty acids, oils, resins, silicone resin, or mixtures thereof. This has the purpose to fix the lithium compound in the molding.
  • the invention is understood by polymer carbon-containing macromolecules. Preference is given to silicones and silicone resins, as well as thermally residue-free decomposable polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol or cellulose and cellulose derivatives.
  • a mixture which comprises at least one thickener, preferably selected from the group consisting of xanthan gum, glycerol, pyrogenic silicas and flame-pyrolytically deposited oxides. It has been found that the use of the abovementioned thickeners is particularly effective for the production of dimensionally stable shaped bodies.
  • the viscosity of the matrix covers the liquid to pasty area, ie a viscosity of 0.5 mPas to 10 6 mPas.
  • the desired viscosities can be achieved by suitable choice of solvent, thickener or matrix and by addition of particles or insoluble components.
  • thermocatalytic reaction at temperatures of 100 0 C to 600 0 C, preferably at 200 0 C to 400 0 C, more preferably at 200 0 C to 350 0 C take place.
  • thermocatalytically active surface may in this case be present on the entire surface of the molding or on parts thereof and be present as a continuously active surface or in the form of small dispersed agglomerations. It is understood by those skilled in the art that in the presence of non-continuous active surfaces, the lithium concentration must be reached only selectively.
  • the lithium-containing surface may be a constituent of the shaped body, be in the form of a coating on the substrate or completely penetrate the shaped body.
  • the lithium compounds can be present as simple salts, but also in the form of mixed salts.
  • the lithium compounds can be used as crystalline or amorphous layers or particles but also in matrices or in other systems, such as e.g. Include zeolites included. It only has to be ensured that some of the lithium compounds are accessible on the surface. If the thermocatalytically active component is not distributed homogeneously in the shaped body, it may be designed such that the shaped body has further possibly functional properties, such as diffusion barriers, which prevent or at least slow down the diffusion of lithium into the substrate.
  • thermo-catalytic activity of the thermo-catalytically active surface can be maintained for a long time. Furthermore, it can also be prevented damage to the shaped body by gases that are released during the catalytic decomposition. Examples include, e.g. Sulfur-containing gases, which may affect the stability of the shaped body, such as a glassy molded body.
  • lithium compounds without integration into a matrix are preferably connected to the substrate by a heat treatment. Some of the lithium compounds mentioned above can be melted the. At higher temperatures, ie greater than 300 0 C, an ion exchange between the molding and lithium can take place.
  • ion exchange reactions on glasses, sintered glasses and ceramics are preferred in which, for example, hydrogen ions are exchanged from the substrate by lithium ions.
  • the ion exchange can take place during the manufacturing process of the glasses, for example in the float process or in glass shaping, or in a downstream heat process.
  • thermocatalytically active component may be formed as a gradient in the surface of the shaped body. In this case, the increase of the lithium concentration towards the surface is to be preferred.
  • the thermocatalytically active molding according to the invention may have micropores with an average pore diameter less than 2 nm, mesopores with a pore diameter of 2 to 50 nm and / or macropores with a pore diameter greater than or equal to 50 nm, preferably 1 to 50 ⁇ m, particularly preferably 10 to 20 ⁇ m.
  • the shaped body has a hierarchical pore structure with, for example, macropores and / or mesopores and / or micropores.
  • Hierarchical pore structure is understood according to the invention to be at least two different pore volumes with preferably narrow pore distributions.
  • the internal surface area after multi-point BET evaluation is 15 to 3000 m 2 / g for the inventive thermocatalytically active molding. In a preferred embodiment, the internal surface area after multi-point BET evaluation is 50 to 1500 m 2 / g, more preferably 250 to 1000 m 2 / g.
  • the cumulative pore volume measured by the BJH method is 0.02 to 2.0 ml / g for the thermocatalytically active molding according to the invention.
  • the BJH Method is used to determine mesopore volumes and distributions.
  • thermocatalytically active surfaces according to the invention can be formed directly in the production of the shaped article or applied to the shaped article by processes known to those skilled in the art.
  • the shaped body is obtained by providing a liquid to viscous or solid mass, shaping this mass, drying and baking.
  • all the skilled person known shaping processes such as the template, extrusion or sintering process, slip casting and foaming applied become.
  • template materials are used for targeted pore formation in the molded body.
  • Template materials are, for example, organic functional groups, organic surfactants such as cetyltrimethylammonium bromide, organic liquids such as camphor or octanol / water mixtures, synthetic organic polymers such as polyvinyl alcohol, polyvinyl chloride, polystyrene, polymethacrylate, phenolic resins, nylon, cellulose acetate, naphthalene, polyurethane, polyamide , Polyethylene oxide, polyethylene glycol, triblock copolymers of, for example, polyethylene and polypropylene units, hydrogels of, for example, polyacrylamide, natural organic materials, such as wood, sponges, coconut, jute, hemp, flax, gelatin, xanthan, glucose, sucrose, dextrose, wax, alginate, starch , Cellulose fibers and fiber fabrics, inorganic materials such as carbon black, carbon fibers and fabrics, metals, salts
  • organic functional groups
  • template materials are introduced, for example, singly or in combination during the liquid-phase-based preparation of the active component and / or the lithium-free filler materials.
  • These template materials are characterized by the fact that the porosity in the thermocatalytically active molding can be adjusted by their shape and surface.
  • the template materials for example, during the molding process again off chemically dissolved out of the molding and / or thermally decomposed.
  • the chemical dissolution of the template materials can be carried out, for example, by means of acid and / or alkali and / or by means of organic solvents.
  • pore sizes from 0.5 nm to 5 mm can be set in a targeted manner.
  • targeted micropores can be prepared via the use of cationic surfactants such as cetyltrimethylammonium bromide as a template molecule.
  • cationic surfactants such as cetyltrimethylammonium bromide
  • mesopores in the size range of 5 to 20 nm can be made by the use of neutral surfactants such as triblock copolymers.
  • Spherical macropores of, for example, 100 nm to 1 ⁇ m pore diameter can be prepared via the use of polystyrene particles as template materials.
  • a regularly ordered pore structure can be produced in addition to the pore size and pore geometry.
  • the pores are formed in the thermocatalytically active molding on the targeted entry of gas bubbles.
  • These foams can be prepared, for example, by the use of oil / water solvent mixtures and / or by organic surfactant additives and / or gas-pressure-based foaming.
  • thermocatalytically active shaped body can be produced by shaping processes such as dry pressing, extrusion or ceramic injection molding (CIM). Characteristic of the dry pressing is the very low residual moisture. It tends to zero.
  • a drying is not required. The process is thus excellently suitable for parts with high dimensional accuracy in large quantities.
  • a pressing tool for axial dry pressing consists of a press die and upper and lower punches. The stamps can additionally be divided several times, depending on the complexity of the component. The pressed granulate is filled into the mold by means of filling shoe. In the case of two-sided pressing, a controlled movement of the upper and lower punches subsequently leads to the compression of the granulate, while only the upper punch moves in the case of one-sided pressing. The pressure is automatically removed via ejector, slide and gripper.
  • Extrusion is the oldest of the three processes in ceramics. Here, the moisture content of the starting material is around 15% to 25%. Shaping takes place both with piston extrusion presses and with vacuum screw presses. The technology offers two proven possibilities: horizontal and vertical extrusion. The extrusion process makes it particularly easy to produce rotationally symmetric parts such as axes or pipes. But even more complicated profiles are feasible with appropriate mouthpiece design.
  • ceramic injection molding offers the most creative freedom. Only in the case of ceramic injection molding can threads, undercuts or diagonal bores be applied directly during molding. Nevertheless, injection molding is still very special in the field of ceramics because it is time-consuming. Mainly because of the relatively long removal of the thermoplastic components required for the process (debindering). However, especially for complex components, ceramic injection molding is indispensable due to the advantages described. Sintering processes are generally carried out with powder masses. Here, powder masses are first formed so that at least a minimum cohesion of the powder particles is given. The pre-pressed green compact is then compacted and cured by heat treatment below the melting temperature. The production of the green compact takes place either by compression of powder masses or by shaping and subsequent drying.
  • the porosity and volume of the green compact decreases significantly.
  • the strength of the sintered bodies is based on the sintering necks formed, which are created by surface diffusion between the powder particles.
  • a calibration of the workpiece is carried out after the last operation, while the quasi-finished workpiece is again pressed under high pressure into a mold.
  • thermocatalytically active component and / or the filler particles are prepared in whole or in part from particles which have an agglomerated particle size of 100 nm to 15 ⁇ m. These particles are preferably produced via precipitation reactions from the liquid phase and / or hydrothermal processes and / or flame pyrolysis and / or CVD processes and / or mechanical painting of ceramic, glass-ceramic and glassy powders.
  • thermocatalytically active component and / or the filler particles are prepared in whole or in part from nanoparticles which have an agglomerated particle size of less than or equal to 100 nm. These particles are preferably prepared via precipitation reactions from the liquid phase and / or hydrothermal processes and / or flame pyrolysis and / or CVD processes.
  • the thermocatalytically active shaped body is formed from a fiber fabric or / and a nonwoven fabric.
  • the thermocatalytically active component may consist of short fibers.
  • the fibers can be produced, for example, by spinning processes known to those skilled in the art, such as, for example, the gas-pressure spinning process, the melt-spinning process or the spin-spinning process. In a particular embodiment, it is assumed that sol-gel precursors are used as spinning masses.
  • the gas-pressure spinning process the production of the fibers, for example, in a commercial spinning plant. In this case, the spinning mass is filled into an optionally coolable pressure cylinder which, for example, has been subjected to an air pressure of 10 to 50 bar.
  • the resulting force presses the sol through nozzles, forming threads.
  • the threads have a diameter of 5 and 100 ⁇ m.
  • the partial or / and complete drying and / or curing of the fibers took place directly after the exit of the fibers from the spinneret, already during the fall of the fibers through the spinning shaft.
  • a chemical hardening by hardening gases is also carried out.
  • the shaped body can also be produced via a melting process.
  • Thermocatalytically active glasses and / or ceramics can be melted, for example, according to the phase diagrams and instructions in the book "Phase Diagrams for Ceramists, The American Ceramic Society, 1995".
  • a shaped body according to the invention can be produced, for example, by slip casting, by first mixing a metal oxide powder as filler with a lithium-containing metal oxide powder. This mixture is in a colloidal sol, here, for example, a lithium zirconate sol consisting of amorphous, molecularly disperse sol-gel particles and crystalline, colloidally disperse nanoparticles, homogenized and suspended to a slurry. The slip can then be poured into a negative mold for the later shaped body.
  • a colloidal sol here, for example, a lithium zirconate sol consisting of amorphous, molecularly disperse sol-gel particles and crystalline, colloidally disperse nanoparticles
  • the mold can be cooled to a temperature below the freezing point of the solvent, that is frozen.
  • the temperature should be well below the freezing point, for example, the slurry is cooled with the mold to -5 0 C to -40 ° C.
  • the slip irreversibly becomes a solid gel (green body).
  • This green body can now be demolded and then thawed.
  • the green body is dried under normal conditions or in an air oven at elevated temperature and sintered, for example under an air atmosphere, so that the thermocatalytically active molded body is formed.
  • the thermocatalytically active molding can be made by coating and / or infiltrating a porous support material with a thermocatalytically active material. The infiltration is preferably carried out under reduced pressure.
  • Porous ceramic or glassy films may also constitute an embodiment of the invention. These films are preferably produced by the tapecasting method known to the person skilled in the art.
  • thermocatalytically active shaped body The coating of individual fibers, fiber bundles or fiber fabrics can also be used to produce a special embodiment of the thermocatalytically active shaped body.
  • An inventive variant of the invention is the production of a ceramic fiber composite material consisting of ceramic and / or glassy fibers, which are optionally provided with a coating and embedded in a ceramic and / or glassy matrix. At least one component of the ceramic fiber composite material consists of a thermocatalytically active material, preference being given to a thermocatalytically active material containing lithium ions.
  • moldings can be provided and filled with the active component, preferably flooded. After drying and baking, the active component is present as part of the component.
  • combustion chamber encompasses any chamber in which a combustion of oxidizable substances, for example of carbon-containing or hydrocarbon-containing or nitrogen-containing substances, takes place. This includes combustion chambers of internal combustion engines, industrial combustion chambers, but also eg open or closed fireplaces or stoves in private households. The term combustion chamber also closes other chambers in which carbonaceous or hydrocarbon-containing substances are exposed to an elevated temperature, such as cooking, roasting and grilling dishes or ovens.
  • the combustion chamber has an exhaust gas outlet, wherein the substrate according to the invention is arranged in the region of the exhaust gas outlet.
  • Such an exhaust outlet may be, for example, a chimney or oven, but also an exhaust of an internal combustion engine, such as in the automobile.
  • the substrate according to the invention can in this case be arranged in the combustion chamber itself or at an interface between combustion chamber and exhaust gas outlet or in the exhaust gas outlet.
  • the temperatures at which catalytic sootburning takes place can be significantly reduced, so that this process is e.g. already takes place at a temperature which usually prevails in a combustion chamber according to the invention, so that additional heating for soot combustion is no longer necessary.
  • carbon black is understood as meaning any particular particulate predominantly carbonaceous agglomeration of material. This includes both products resulting from the incomplete combustion of carbonaceous or hydrocarbon-containing substances as well as other carbonaceous agglomerations that arise, for example, from a thermal treatment of fuels. It is clear to the person skilled in the art that carbon, in addition to carbon, also has other properties. may contain constituents such as unburned hydrocarbons, sulfur compounds, phosphorus compounds, nitrogen compounds or metals and metal compounds.
  • carbon black food residues ie food residues of a substance or of a substance mixture, which firmly bonds to the surface at the operating temperatures of the cooking, frying, baking and grilling devices and optionally at least partially into the self-cleaning surface or in it optionally present pores, understood.
  • These may be liquid / greasy oils at the operating temperatures, aqueous phases (salt and sugar solutions) as well as these mixed carbohydrates and proteins.
  • the impurities are oils and fats such as sunflower oil, soybean oil, vegetable fat, olive oil, lard, and tomato sauce, cheese, fruit juices, and milk.
  • the shaped body according to the invention can be used in the following applications:
  • incinerators such as waste incinerators, power plants, crematoria;
  • reactors such as chemical reactors, refineries
  • thermocatalytically active shaped bodies nonwoven fabric
  • the solution was single-phase and contained no solids.
  • the viscosity was 1 Pas.
  • the sol-gel mass showed no discernible solid phase portions.
  • the homogeneous sol-gel mass could be spun into fibers. It is also referred to as a dope.
  • the production of the fibers was carried out for example in a commercially available spin line.
  • the dope was filled in an optionally coolable pressure cylinder, which was acted upon by an air pressure of 20 bar.
  • the resulting force pressed the sol through nozzles, forming threads. Depending on the diameter of the nozzle, the threads had a diameter of 5 and 100 ⁇ m.
  • the fibers were dried by means of an NIR emitter and then annealed as a nonwoven fabric in a convection oven for 30 min at 600 0 C.
  • the nonwoven fabric obtained in this way could be used directly as a thermocatalytically active molding or as a thermocatalytically active component of a thermocatalytically active molding.
  • a ceramic sol-gel slurry consisting of an amorphous molecularly dispersed sol-gel binder, crystalline nanoparticles and ceramic particles was prepared.
  • the finished ceramic slip was composed of 20% by weight of the sol gel. Binders, 20 wt .-% of the nanoparticles dissolved in the sol-gel binder and 60 wt .-% of ceramic particles together.
  • the ceramic slurry was then used to infiltrate a flax fiber fleece. The drying took place at 150 ° C. for 1 h. The final heat treatment was carried out at 650 ° C.
  • amorphous sol-gel precursor 1.5 mol of acetylacetonate, 1 mol of zirconium tetrapropylate were initially charged with 100 g of concentrated acetic acid, and 2 mol of lithium acetate * 2 H 2 O in 100 g of ethanol were added.
  • 1 mol of acetylacetonate was reacted with 1 mol of zirconium tetrapropylate and then hydrolyzed with 3 mol of water. After cooling the solution, the solvent was removed on a rotary evaporator to obtain an amorphous zirconia precursor powder.
  • the ceramic particles For the preparation of the ceramic particles, 20 g of lithium acetate dihydrate in 100 g of ethanol were mixed with 10 g of concentrated acetic acid. This solution was then added dropwise to 46 g of zirconium tetrapropylate in 50 g of acetone. After the solution is gelatinized after 24 hours, the gel was annealed at 500 ° C. for 3 hours and 700 ° C. for 2 hours. The ceramic particles were then comminuted by mechanical grinding to a particle size less than 10 microns.
  • a ceramic sol-gel slurry consisting of an amorphous molecularly dispersed sol-gel binder, crystalline nanoparticles and ceramic particles was prepared.
  • the finished ceramic slip was composed of 20% by weight of the sol gel. Binders, 30 wt .-% of the nanoparticles and 50 wt .-% of ceramic particles together.
  • a cylindrical green body was cast with a diameter of 10 cm. The drying and gelation took place over 24 h at room temperature and a relative humidity of 20%. The annealing followed at 700 0 C for 2 h.
  • amorphous sol-gel precursor 1.5 mol of acetylacetonate, 1 mol of zirconium tetrapropylate were initially charged with 100 g of concentrated acetic acid, and 2 mol of lithium acetate * 2 H 2 O in 100 g of ethanol were added.
  • the ceramic particles For the preparation of the ceramic particles, 20 g of lithium acetate dihydrate in 100 g of ethanol were mixed with 10 g of concentrated acetic acid. This solution was then added dropwise to 46 g of zirconium tetrapropylate in 50 g of acetone. After the solution is gelatinized after 24 hours, the gel was annealed at 500 ° C. for 3 hours and 700 ° C. for 2 hours. The ceramic particles were then comminuted by mechanical grinding to a particle size less than 5 microns.
  • a ceramic sol-gel slurry consisting of an amorphous molecularly dispersed sol-gel binder, amorphous nanoparticles and ceramic particles was prepared.
  • the finished ceramic slip was composed of 25% by weight of the sol-gel binder, 25% by weight of the nanoparticles and 50% by weight of ceramic particles.
  • a cylindrical green body was cast with a diameter of 12 cm.
  • the drying and gelation took place over 24 h at room temperature and a relative humidity of 20%.
  • the annealing followed at 650 0 C for 2 h.
  • the amorphous sol-gel precursor and the ceramic particles were prepared as described in Example 3. Commercially available amorphous SiO 2 particles were used as nanoparticles.
  • thermocatalytically active shaped article was produced in such a way that loose or lightly bound thermocatalytically active particles were fixed in an outer mold.
  • two types of particles were mixed and filled into a cylinder with closable ends on both sides. The end surfaces were porous, so that gases can flow through the molding.
  • the powders were shaken and lightly pressed so that any air pockets were avoided.
  • One type of particle was prepared by ion exchange on zeolites.
  • 10 g of zeolite of the type Y 24 h at 80 0 C in 1 liter of 1-molar lithium chloride solution were stored. After completion of the ion exchange, the zeolite was filtered off and washed with water which had been adjusted to pH 9 with LiOH.
  • solution A For the second type of particles, two solutions were first prepared. For this, 20.4 g of lithium acetate * 2 H 2 O in 20 g of acetic acid and 100 g of ethanol were mixed (solution A). For the second solution, 49.2 g of aluminum sec-butoxide were mixed in 50 g of isopropanol (solution B). Subsequently, solution A was added with stirring to solution B and made up to 250 ml with ethanol. After 2 hours the material gelled white and was then dried in three steps at 100 ° C for 16 h, annealed at 400 0 C for 3 h and 700 0 C for 3 h. The gel was crushed with a mortar to form fine particles.
  • 125 mg of catalyst mass was flowed through with a feed stream of 1% CO and 0.5% O 2 in helium at a gas flow rate in the educt of 183.3 ml / min.
  • the temperature of the sample chamber was successively increased to 500 0 C.
  • the CO 2 concentration in the gas outlet stream was measured and evaluated as a measure of the percentage conversion of CO.
  • 125 mg of catalyst mass was flowed through with a feed stream of 1000 ppm propene and 4500 ppm O 2 in helium at a gas flow rate in the starting material of 183.3 ml / min.
  • the temperature of the sample chamber was successively increased to 500 0 C.
  • the CO 2 concentration and CO concentration were measured in the gas outlet stream and evaluated as a measure of the propene conversion.
  • 125 mg of catalyst mass was flowed through with a feed stream of 1000 ppm of NO and lOOOppm CO in helium at a gas flow rate in the educt of 183.3 ml / min.
  • the temperature of the sample chamber was successively increased to 500 0 C.
  • the CO 2 , CO, NO and N 2 O concentrations were measured in the gas outlet stream.
  • the following table shows, by way of example, the light-off temperatures (50% conversion) of the gas reactions and the temperatures of the complete soot combustion.
  • moldings with agglomerated particles are understood as meaning a technically produced aggregation of individually present grains, particles or pieces of material, in which, for example, the catalytically active particles are connected by means of a shaping process.
  • particles and / or particle mixtures are connected to one another via sintering necks in the sintering process, via binding matrices, such as organic binders and / or inorganic binders, such as glass and / or sol gel, and / or via physical binding forces.
  • binding matrices such as organic binders and / or inorganic binders, such as glass and / or sol gel, and / or via physical binding forces.
  • the particle sizes of the particles are not defined in the sense of the invention, but can be chosen freely and have different size distributions.

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Abstract

La présente invention concerne un corps moulé à action thermo-catalytique se composant d'au moins deux constituants mélangés, au moins l'un des constituants se composant d'au moins un composé de lithium ou comprenant au moins un composé de lithium et, dans la mesure où un composé de lithium est Li2O, au moins un autre composé de lithium qui n'est pas Li2O, étant présent. L'invention a également pour objet un procédé de réalisation du corps moulés à action thermo-catalytique et son utilisation.
PCT/EP2010/004928 2009-08-13 2010-08-12 Corps moulé à action thermo-catalytique, procédé permettant sa réalisation et son utilisation Ceased WO2011018219A2 (fr)

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