EP1613359A1 - Systeme catalyseur pour supprimer les odeurs - Google Patents

Systeme catalyseur pour supprimer les odeurs

Info

Publication number
EP1613359A1
EP1613359A1 EP04723177A EP04723177A EP1613359A1 EP 1613359 A1 EP1613359 A1 EP 1613359A1 EP 04723177 A EP04723177 A EP 04723177A EP 04723177 A EP04723177 A EP 04723177A EP 1613359 A1 EP1613359 A1 EP 1613359A1
Authority
EP
European Patent Office
Prior art keywords
particles
coating
catalyst system
catalyst
odor
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
EP04723177A
Other languages
German (de)
English (en)
Inventor
Thomas Copitzky
Frank JÖRDENS
Jürgen Salomon
Gerhard Schmidmayer
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.)
BSH Hausgeraete GmbH
Original Assignee
BSH Bosch und Siemens Hausgeraete GmbH
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 BSH Bosch und Siemens Hausgeraete GmbH filed Critical BSH Bosch und Siemens Hausgeraete GmbH
Publication of EP1613359A1 publication Critical patent/EP1613359A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C15/00—Details
    • F24C15/005—Coatings for ovens
    • 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
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles

Definitions

  • the present invention relates to a catalyst system for cooking, roasting, baking and grilling devices.
  • the invention also relates to a device for cooking, roasting, baking and / or grilling, comprising such a catalyst system.
  • DE-A 39 42 236 describes coating agents in cooking, baking, roasting and grilling devices. These are characterized by a content of oxides of at least one metal from the group cerium, sodium, potassium calcium, manganese, nickel and cobalt, but can also contain alkali and / or alkaline earth metal compounds with tantalum oxide, niobium oxide and / or tin dioxide. DE 39 42 236 also describes coating agents in cooking, baking, roasting and grilling devices based on borides, carbides, silicides or nitrides of metals from the 4th, 5th or 6th subgroup of the PSE (e.g. molybdenum disilicide).
  • PSE molybdenum disilicide
  • the coating composition required for the production of such a coating comprises a (1) polycondensate from a silane or an oligomer derived therefrom, optionally a compound of glass-forming elements and (2) particles from one or more transition metal oxides, the weight ratio of transition metal oxide particles to polycondensate 10: 1 to 1:10.
  • transition metal oxides are the oxides of La, Ce, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag or Zn.
  • the coating composition can inorganic particles in the nanometer or micrometer Scale, especially in the form of a sol, can be added.
  • Preferred inorganic particles are Al 2 0 3 , Si0 2 , Sn0 2 , iron oxides and C (graphite, carbon black).
  • the size ratios for the nanoscale particles are such that the average particle size (diameter) is up to 300 nm. However, up to 50 or up to 100 nm are preferred.
  • DE-A 28 28 613 describes a self-cleaning coating for cookers, which has a porous layer of a base of an inorganic binder with a matting agent on the surface, particles of a catalyst distributed in this layer (which tends to change color as a result of its catalytic action change) and contains a non-discoloring substance.
  • the catalytic effect is achieved by at least one of the metal oxides of Mn 2 0 3, Mn0 2 or CuO and / or by a solid acid catalyst, such as zeolite.
  • a suitable group of non-discoloring substances are accordingly ferrites, for example Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , ZnO, CaO or MgO are proposed as matting agents.
  • the inorganic binders mentioned include frits made from borosilicate glass, phosphate and lead frits and alkali metal silicates.
  • a coating film formed of a composition containing an oxidation catalyst, a synthetic silicone resin as a binder and an organic solvent (LM) is formed on the article, which is to be self-cleaning, by heating the composition to 300 to 400 ° C.
  • the catalyst is preferably a noble metal, a metal oxide or a mixture of two or more metal oxides, in particular Pt, Pd or Mn0 2 , a Cu oxide, an Fe oxide, a Ni oxide or a Cr oxide.
  • a coating containing an inorganic polymerization inhibitor for producing self-cleaning surfaces is described in DE-C 30 19 828.
  • the coating composition required for the production of the coating is dispersed in a liquid binder which contains an oxidation catalyst (metal or metal oxide) and the polymerization inhibitor mentioned.
  • Liquid binders are particularly popular in silicone resins dissolved in organic solvents.
  • Polymerization inhibitors are in particular Al (OH) 3 , Sb 2 0 3 , phosphate frit material or a mixture of at least two of these, and metal oxides / metals are oxides of V, Cr, Mo, Mn, Ni and Cu, especially Mn0 2 , Ni 2 0 3 , CuO, or Pt or Pd, especially colloidal Pt or Pd on Al 2 0 3 .
  • odor catalysts in the exhaust air duct which have an additional heating, and thus record all components of the exhaust air via the temperature field at very high temperatures of 300-500 ° C.
  • a typical example of this is the catalyst described in DE-A 199 15 377.
  • Catalytic converter systems that require additional heating have a negative impact on the energy consumption of the devices.
  • the ability to self-clean without additional heating decreases relatively quickly when the catalytic converters are occupied by food residues.
  • the quality and durability of the self-cleaning coatings / layers of cooking, roasting, baking and grilling devices can be determined using DIN ISO 8291 with a layer thickness of at least 150 ⁇ m.
  • the coatings known in the prior art can withstand 5-10 cycles of dropping soybean oil and subsequent heating to 250 + 10 ° C. before the surface becomes laked (assessment according to DIN ISO 8291 due to the appearance of gloss).
  • the catalyst mixtures based on Cu, Co, Ni contained in the catalytically active coatings according to the prior art are not physiologically harmless, those based on noble metals and Ce are economically uninteresting, since they are too expensive.
  • the inventors achieved this object by means of the catalyst system of the present invention consisting of the combination of (i) and (ii) as described below.
  • the present invention relates to a catalyst system for cooking, roasting, baking and grilling devices, comprising (i) a simultaneously self-cleaning and odor-reducing coating having a structure composed of (a) porous particles A and (b) a binder, wherein the porous particles A have no solid or liquid second phase in their pores a, and (ii) a customary odor catalyst, for example based on metal oxide.
  • the present invention relates to an appliance for cooking, roasting, baking and / or grilling, e.g. a cooking oven comprising such a catalyst system.
  • the invention relates to a catalyst system in which the coating (i) is applied to elements of the device which are contaminated directly with food and / or the odor catalyst (ii) is located in the exhaust air duct of the device.
  • porous metal oxides such as thermally and chemically stable, porous metal oxides, carbides or nitrides as porous particles A.
  • the porous particles A Si0 2 , Ti0 2 , Al 2 0 3 , Zr0 2 , SiC, Si 3 N, C and B 2 0, preferably ⁇ -Al 2 0 3 and Si0 2 .
  • the size of the particles A is 5 to 100 ⁇ m, in particular 10 to 80 ⁇ m, 20 to 60 ⁇ m or 30 to 50 ⁇ m.
  • Another preferred embodiment of the catalyst system according to the invention provides open-cell pores a of particles A.
  • the binder of the coating (i) is an inorganic substance and permanently temperature-resistant up to 500 ° C., in particular an inorganic polymer such as a silicone resin or an inorganic sol, both based on
  • the binder particles have one
  • Diameters from 0.5 to 10 ⁇ m, in particular from 1 to 5 ⁇ m.
  • the coating (i) additionally contains other types of particles, in particular particles which reduce the roughness of the coating, improve the bond on the one hand between the particles A and on the other hand between the coating and the substrate, and adjust the Color or improve thermal degradation, haptics or spreading ability.
  • These other particles of coating (i) can e.g. nanoscale particles (particles B '), particles in the micrometer range (particles B), colored body particles, metals, in particular transition metals, or metal oxides, in particular transition metal oxides.
  • the coating (i) has no oxide of a subgroup metal, in particular no physiologically incompatible oxide of a subgroup metal.
  • the particles B and B 'of the coating (i) are thermally and chemically stable.
  • These are in particular metal oxides, carbides and nitrides such as Si0 2 , TiQ 2 , Al 2 0 3 , Zr0 2 , SiC, Si 3 N 4 and B 2 0 3 .
  • metal oxides, carbides and nitrides such as Si0 2 , TiQ 2 , Al 2 0 3 , Zr0 2 , SiC, Si 3 N 4 and B 2 0 3 .
  • a special version of the coating (i) is described below as ecolysis.
  • this ensures that contaminated air repeatedly reaches or gets into the odor-reducing coating (i) and can thus be cleaned effectively (the efficiency is increased).
  • a further cleaning stage is brought about by the odor catalyst (ii), which is advantageously positioned in the exhaust air duct. Since the odor catalyst (ii) is not in direct contact with the food in this case and the surface area is the smaller coating, according to the invention there are expensive and / or physiologically questionable components (for example metal oxides, in particular noble metal oxides) instead of preferred in the coating (i). However, they (the metal oxides) are required to a far lesser extent than if the odor catalyst (ii) were used without the combination with the coating (i). Additional heating in the exhaust air duct is not necessary, but can nevertheless be provided.
  • Odor catalyst (ii) in the sense of the present invention is any surface described in the prior art which suppresses or breaks down odors by adsorbing organic molecules from the gas phase and, if appropriate, their subsequent catalytic decomposition, for example - possibly heatable - zeolites, clays, aerogels , Activated carbon or ceramic or metal carrier, which can be designed in a sponge or honeycomb structure or as a film. Also the above Materials are used as bulk goods. These carrier materials can additionally be coated, the catalytically active portion of the coating being based on noble metals, lanthanides, actinides, oxides or mixed oxides of these or other (main group / sub group / transition) metals.
  • the olfactory catalyst is (ii) a catalytic composition which can be prepared from a coating composition comprising (1) a polycondensate of a silane or an oligomer derived therefrom, optionally a compound of glass-forming elements and (2) particles of one or more transition metal oxides, the weight ratio of transition metal oxide Particle to polycondensate is 10: 1 to 1:10.
  • a coating composition comprising (1) a polycondensate of a silane or an oligomer derived therefrom, optionally a compound of glass-forming elements and (2) particles of one or more transition metal oxides, the weight ratio of transition metal oxide Particle to polycondensate is 10: 1 to 1:10.
  • the transition metal oxide (s) of the odor catalyst (ii) is / are made from the oxides of La, Ce, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag and Zn selected.
  • the olfactory catalyst (ii) of the catalyst system is unheated.
  • a preferred odor catalyst (ii) is the catalyst described in DE-A 199 15 377 and 199 15 378.
  • the coated surface of the cooking, roasting, baking or grilling device or its parts remains mechanically resilient, that is, the adhesion of the coating (i) to its substrate, its impact resistance, its chemical resistance, its Resistance to temperature changes and their scratch resistance must be satisfactory, which is achieved according to the invention.
  • contamination or food residue is understood to mean a food residue that is liquid enough at the operating temperatures of the cooking, roasting, baking and grilling device to penetrate into the structure of the self-cleaning coating (i).
  • These can be liquid fats / oils, aqueous phases (e.g. salt solutions) and carbohydrates / proteins mixed with them at the operating temperatures.
  • the impurities are also introduced into the coating (i) in the form of aerosols or gases via air transport.
  • the coatings (i) are provided with thermally (permanently up to 500 ° C.) and chemically stable, porous, inexpensive and physiologically compatible oxides, in particular metal oxides, but also such stable carbides and nitrides.
  • Preferred oxides are Zr0 2 , Al 2 0 3 and Si0 2 .
  • the thermal degradation and thus the self-cleaning and odor-reducing power of the usual coatings of parts on or in cooking, roasting, baking or grilling devices is limited because the food residues on the solid phase do not come into contact with enough oxygen for the reduction of the impurities to (ideally) C0 2 and H 2 0 is necessary.
  • the inventors have therefore made available layers with structures into which the impurities penetrate, in which they can be spread and ideally completely broken down to C0 2 and H 2 0.
  • the coating to be produced (i) with the ability to self-clean and reduce odor consists of at least one type of particle A with open porosity.
  • the size of the particles is 5 to 100 ⁇ m. Preferred sizes are 10 to 80 ⁇ m, 20 to 60 ⁇ m and 30 to 50 ⁇ m.
  • the pores a in the particles A are either in the order of magnitude that the impurities cannot penetrate, experience has shown that they are less than 1 ⁇ m, preferably 0.1 to 0.6 ⁇ m. In the case of larger pores with a> 1 ⁇ m, the particles A are coated with a porous membrane (pores c). This membrane prevents the penetration of impurities into the porous particles A.
  • the membrane has only the purely binding function, ie in such a case the membrane does not necessarily have to be porous.
  • the particles A are not completely coated, but are preferably provided with the binder only at the contact points between two adjacent particles A. This guarantees that as many of the pores a as possible remain accessible to air.
  • the particles A are thermally and chemically stable, porous oxides, in particular metal oxides, carbides or nitrides.
  • Exemplary representatives are the substances listed below for particle B.
  • ⁇ -Al 2 O 3 and SiO 2 are particularly preferred as particles A.
  • the spaces between the particles A are responsible for the penetration and spreading of the liquid food residues in the coating (i).
  • the aim is the best possible distribution / spreading of the contaminants in the coating (i) in order to maximize the area of attack for thermal degradation.
  • the size distribution of the pores b is essentially determined by the size of the particles A and the volume fraction of their binding phase.
  • the amount of the binder to be used can easily be determined by routine tests if it is taken into account that the amount which is most advantageous according to the invention is so large that spreading in the pores b on the one hand and adequate mechanical properties (scratch resistance, adhesion to the substrate) on the other hand the coating (i) are guaranteed.
  • the volume fraction of the binding phase is 5-40%, preferably 20-30% or 15-25%.
  • the pores b between the particles A are significantly larger than the pores a, so that impurities can penetrate and spread into the structure. That way ensures that there is always (enough) oxygen for thermal degradation in contact with the contaminants to be removed, especially since the pores a regenerate again and again, ie can absorb air.
  • All pore systems mentioned according to the invention i.e. the pores a and b, but also the pores of the binder, if present, are open-pored.
  • the coating composition which forms the basis for the coating (i) to be produced according to the invention may, however, also contain further types of particles which (a) reduce the roughness of the coating (i) and improve the feel, (b) the improvement serve as a bond between particles A and between coating and substrate, (c) adjusting the color or (d) improving thermal degradation or spreading capacity (to name just a few examples).
  • particles which fall under (a) but also (b) are nanoscale particles (particle B '), particles in the micrometer range (particle B) and color body particles (eg spinels):
  • An example of (c) are spinels, and finally, physiologically harmless, oxides of transition metals, especially the oxides of Zr and Ti, are an example of (d).
  • particles B and B ' their chemical composition is of no further importance.
  • the particles are thermally and chemically stable. They may, but need not, be porous.
  • Suitable substances as nanoscale or micrometer particles are oxides, especially metal oxides, carbides and nitrides, for example Si0 2 , Ti0 2 , Al 2 0 3 , Zr0 2 , SiC, Si 3 N 4 and B 2 0 3 , in particular ⁇ - AI 2 0 3 .
  • the choice of the material composition of the particles B and B ' is not dependent on the chemical composition of the particles A.
  • the particles B and B' can also be Al 2 0 3 , but just as well Si0 2 , Ti0 2 , Zr0 2 , SiC, Si 3 N 4 , B 2 0 3 or a spinel (or another stable component). Preferred are all such particles that are inexpensive and harmless to health.
  • the sizes of the particles B and B ' are important.
  • the nanoscale particles B ' have a diameter of up to 100 nm, but are advantageously only 20 to 60 nm.
  • the particles in the micrometer range instead have a diameter of 0.5 to 10 ⁇ m, with the additional restriction for these particles B that they are at least five times, but at most 20 times smaller than the particles A.
  • the pores a are free of solid or liquid second phases. This applies to the time the cooking, roasting, baking and grilling device is used, but also to the unused device.
  • the pores a have no metal oxide, no color body, no particles B or B 'and also no impurities (except those in the gaseous state).
  • the pores a are either sufficiently small so that non-gaseous impurities when using the device on the one hand and metal oxide, colored bodies, particles B or B ′ etc. during the production of the coating (i) on the other hand cannot penetrate into the pores a, or prevented from penetrating into the pores a by means of the porous membrane (pores c) described above.
  • the atmospheric oxygen in the pores a is also available for the thermal degradation of the contaminants.
  • the above-mentioned porous membrane is a porous adhesive (hereinafter also referred to as a porous binder) or consists of such. It is an inorganic temperature-resistant binder, preferably an inorganic polymer (eg silicone resins and polymeric phosphates) or an inorganic sol, both based on eg Al 2 0 3 , Si0 2 , Ti0 2 , Zr0 2 , P 2 0 5 , SiC, Si 3 N 4 or B 2 0 3 or mixtures of these.
  • an inorganic temperature-resistant binder preferably an inorganic polymer (eg silicone resins and polymeric phosphates) or an inorganic sol, both based on eg Al 2 0 3 , Si0 2 , Ti0 2 , Zr0 2 , P 2 0 5 , SiC, Si 3 N 4 or B 2 0 3 or mixtures of these.
  • the adhesive / binder examples include glass (for example open-cell but also dense glass) which has only been heated to its softening point (T E ) or to a temperature slightly below T E , and silicates such as clays or water glass.
  • the size of the binder particles in the case of a sol is known to be 100 nm or less, and the diameter of the particles can be 5 to 100 nm, preferably 20 to 80 nm. In the event that a binder based on glass or clay etc. is used, diameters of 0.5 to 10 ⁇ m, in particular 1 to 5 ⁇ m, are preferred according to the invention.
  • the coating (i) has a customary metal or metal oxide catalyst (oxidation catalyst and / or polymerization inhibitor) which:
  • basically all of the catalysts described in the prior art for the self-cleaning of ovens are suitable as metal or metal oxide or oxidation catalysts / polymerization inhibitors.
  • the metal oxide or the mixture of the metal oxides has particle sizes of less than 100 nm up to 0.5, 1 or even 2 ⁇ m. According to a preferred embodiment of the present invention, however, it has particle diameters of well below 1 ⁇ m.
  • the particle diameter is preferably 500 nm or less, 300 nm or less, 200 nm or less, and particularly preferably 100 nm or less.
  • a further embodiment of the present invention consists in adding one or more substances to the oxidation catalyst / polymerization inhibitor which lowers / lowers the temperature at which the oxidation catalyst / polymerization inhibitor has a good conversion rate to temperatures of 200 to 250 ° C.
  • This temperature usually corresponds to the working temperatures in the cooking space of the cooking, roasting, baking and grilling devices.
  • Substances in the sense of this configuration are elements of the 1st and 2nd main group of the PSE, i.e. e.g. Sodium, potassium, magnesium, calcium or strontium.
  • the coating composition according to the invention contains an inorganic color body or a non-discoloring material which ensures that any color changes which occur as a result of a change in the value of the metal of the catalyst are covered.
  • Suitable inorganic color bodies are in particular spinels such as MgAI 2 0 4 , MgFe 2 0 4 , MnFe 2 0, FeAI 2 0 4 , NiAI 2 0 4 or MgCr 2 0 4 .
  • Other suitable non-discoloring materials are SiC and graphite.
  • the particle diameter of the optionally used color bodies is 0.2 to 5 ⁇ m, preferably 0.5 to 3 ⁇ m.
  • the coating has optical sprinkling or granitization in order to conceal any optical dirt.
  • sprinkling only one color component is used; in the case of granitization, at least two color components are used.
  • Suitable color components are, for example, spinels, but also Al 2 0 3 , Ti0 2 , Zr0 2 and mixtures of these. The diameter of these components is 50 to 2000 ⁇ m.
  • a nanoscale sol-gel binder based on Ti0 2 or TiO x as spinels a spinel (MnFe 2 0 4 ) microns with a diameter of 1-3 and a size of 500-1000 used as mottling Ti0 2 microns.
  • the particles A have a size of 30-50 ⁇ m and are used in an amount of 50-80, in particular 60-70% by weight.
  • the particles B have a size of 0.7-1 ⁇ m and are used in an amount of 10-20% by weight, especially 15-20% by weight.
  • the sol-gel binder makes up 7-15% by weight, especially 10% by weight, the colored body and the speckle each make up 1-3% by weight, 2 and 1% by weight being particularly advantageous values are.
  • the thickness of the coating (i) is at least 50 ⁇ m, preferably 100 to 500 ⁇ m, but thicknesses of 150 to 450 ⁇ m, particularly from 200 to 400 ⁇ m or 250 to 350 ⁇ m, are particularly preferred. Larger layer thicknesses are technically feasible and also useful, but are of little interest for economic reasons. If, on the other hand, the thickness of the coating (i) is less than 50 ⁇ m, it does not offer a sufficiently large pore volume of the pores a, b and possibly c for the absorption of impurities (only in pores b) and air (in Pores a, b, c).
  • the surface to be coated is enameled surfaces, for example enameled steel, that is a steel which is provided with an enamel layer with a thickness of the order of 100 ⁇ m, which serves to protect against corrosion.
  • enameled surfaces for example enameled steel, that is a steel which is provided with an enamel layer with a thickness of the order of 100 ⁇ m, which serves to protect against corrosion.
  • the pores a remain free of any solid phase and thus have maximum absorption capacity for air. This can be achieved in particular in that the particles used (color bodies, particles B and B ', metal oxide etc.) are not significantly smaller than the pores a.
  • Another way to keep the pores a free of solid phase is to use particulate systems. Because of their zeta potential, the particles do not penetrate the pores, although or even if the latter are significantly larger than the particles.
  • the particles A for example Al 2 O 3
  • an aqueous or organic (alcoholic) binder the binder must never be dissolved, since in this case the pores a of the particles A with a solid phase
  • the binder must never be dissolved, since in this case the pores a of the particles A with a solid phase
  • the binder must never be dissolved, since in this case the pores a of the particles A with a solid phase
  • the cooling step from variant 1 is followed by spraying on the metal oxide catalyst (MeO or Me 2 0), for example in the form of a (particulate) dispersion of metal oxide or metal hydroxide or metal oxyhydroxide (eg Me 2 0 ( OH) 2 ) on.
  • the metal oxide catalyst Mo or Me 2 0
  • the removal of the LM and the optional transfer of the salts into the oxide form is done thermally.
  • the particles A are optionally first mixed with particulate metal oxide, metal hydroxide or metal oxyhydroxide or with particles B and / or B '.
  • the mixture is then dried and calcined, whereupon a powder which may contain MeO or Me 2 0 is obtained.
  • This powder is then, as in the first variant, with an aqueous or organic (alcoholic) dispersed binder (it must not be Be a solution) and possibly an inorganic color body (eg a spinel) and other additives to form a slip which is applied to the surface to be coated and dried there to form a biscuit.
  • a firing takes place at 500 to 800 ° C, at which the layer is solidified and volatile components are expelled if necessary.
  • the fourth variant finally corresponds to variant 3, with the restriction that the particles A are coated or sealed with an organic polymer (for example cellulose) so that they can subsequently be brought into contact with a solution of a metal nitrate without the pores a filled with metal nitrate (after firing with metal oxide) or other slip components.
  • the heating not only converts the metal nitrate to metal oxide, but also the cellulose is pyrolyzed.
  • the further steps are identical to those of variant 3, i.e. a slip is prepared with dispersed binder.
  • the slip can be applied electrophoretically, by spraying or by immersion.
  • the enamel softens so that an improved adhesion between substrate and coating (i) is achieved by sinking the layer.
  • the odor reduction with regard to the test substances was determined in accordance with the guideline VDI 4300, sheet 6, or DIN EN ISO 16017-1 (volatile organic compounds (VOC) in the indoor air) by gas chromatographic analysis of the indoor air.
  • VOC volatile organic compounds
  • the following test was first carried out with a stove without any catalytic coating: 15.0 mg pyrazine, 100 mg maltol, 100 mg vanillin are used in a hermetically sealed test room (16 m 3 ) under the conditions specified (temperature, duration, type of heating) and 50 ⁇ l of 2,4-decadienal are evaporated, an aliquot of the ambient air is collected on a thermodesorption tube, the analytes are determined after thermodesorption by GC / MS and the corresponding areas in the chromatogram are set to 100% using two internal standards.
  • the oven of a built-in oven with a conventional catalytic coating (the catalytic enamel is the commercial grade CK 700/2 from DOM-Email, Cologne) serves as a comparison test. No catalyst is installed in the fumes downstream of the furnace.
  • the test substances (2,4-decadienal as a representative for fats, maltol, vanillin and pyrazine) are evaporated at 180 ° C in the 3D circulating air mode and a room air sample on a for 60 min Thermodesorption tubes collected. The same procedure is followed with an unprepared stove under identical conditions.
  • the surface area of the analytes is normalized using an internal standard and compared with one another by setting the surface area from the test with the unprepared stove equal to 100% and determining the percentage degradation rate - relating to the individual test substances - by difference ,
  • the following degradation values were determined for the conventional catalyst: pyrazine 0%; 2,4-decadienal 24%, maltol 62%, vanillin 25%.
  • No physiologically questionable catalysts were used.
  • No catalyst is installed in the fumes downstream of the furnace.
  • the further test execution and evaluation is carried out analogously to experiment A, with the stoves in experiment B in the top heat / bottom heat mode were operated at 310 ° C for 60 min. The following, significantly better breakdown rates resulted: pyrazine 28%; 2,4-decadienal 63%, maltol 71%, vanillin 64%.
  • An odor catalyst as described in DE-A 199 15 378, is installed in the exhaust air duct of a built-in oven without a catalytic coating. No changes are made to the air balance on the device. The cooker is again operated in the top heat / bottom heat mode at 310 ° C for 60 min. The odor-reducing effect was determined as usual. The breakdown rates were as follows: pyrazine 28%; 2,4- Decadienal 45%, Maltol 55%, Vanillin 46% ..
  • coating (i) a coating according to the present invention.
  • No physiologically questionable catalysts were used.
  • the catalyst according to DE-A 199 15 378 from Example 3 is installed in the waste gas effluent from the furnace.
  • the further test execution and the evaluation took place at 180 ° C and 60 min operating time in the operating mode 3D-circulating air.
  • the efficiency of the cleaning system according to the invention with regard to the breakdown of pyrazine, 2,4-decadienal, maltol and vanillin in the exhaust air surprisingly clearly exceeds the efficiency of the other systems (from experiments A-C).
  • the odor reduction (degradation rate) is 88% for pyrazine, 98% for 2,4-decadienal, 100% for Maltol and 99% for vanillin.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Biomedical Technology (AREA)
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Abstract

L'invention concerne un système catalyseur destiné à des appareils à cuisiner, à rôtir, à cuire et à griller et comprenant (i) un revêtement ayant une structure constituée (a) de particules poreuses A et (b) d'un liant, les particules poreuses A ne présentant dans leurs pores a aucune phase secondaire solide ou liquide, et (ii) un catalyseur d'odeurs qui réduit ou supprime les odeurs par adsorption de molécules organiques de la phase gazeuse et, éventuellement, par leur décomposition catalytique consécutive.
EP04723177A 2003-03-31 2004-03-25 Systeme catalyseur pour supprimer les odeurs Ceased EP1613359A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10314513A DE10314513A1 (de) 2003-03-31 2003-03-31 Katalysatorsystem zum Geruchsabbau
PCT/EP2004/003185 WO2004087223A1 (fr) 2003-03-31 2004-03-25 Systeme catalyseur pour supprimer les odeurs

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EP1613359A1 true EP1613359A1 (fr) 2006-01-11

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DE102007016946A1 (de) 2007-04-05 2008-10-09 Nano-X Gmbh Beschichtungsmaterial mit einer katalytischen Aktivität und Verwendung des Beschichtungsmaterials
DE102007034633A1 (de) 2007-04-05 2009-01-29 Nano-X Gmbh Beschichtungsmaterial mit einer katalytischen Aktivität und Verwendung des Beschichtungsmaterials
DE102010016465B4 (de) * 2010-04-15 2017-08-17 Ceranovis Gmbh Verfahren zur Beschichtung, Beschichtungszusammensetzung und deren Verwendung zur katalytischen Abgasreinigung
DE102014217636A1 (de) * 2014-09-03 2016-03-03 BSH Hausgeräte GmbH Betreiben eines Speisenbehandlungsgeräts
KR101982018B1 (ko) 2015-12-21 2019-05-24 주식회사 에프티넷 리튬 조촉매를 첨가하여 촉매의 활성도를 증가시킨 촉매 코팅 필터
DE102017211289A1 (de) 2017-07-03 2019-01-03 BSH Hausgeräte GmbH Koch-, Brat-, Back- oder Grillgerät mit funktioneller Beschichtung, sowie Verfahren zur Erneuerung der Beschichtung
BR112022008684A2 (pt) * 2019-11-15 2022-07-19 Electrolux Appliances AB Cobertura de ventilador com um revestimento antiaderente e/ou antiumidade, aparelho de cozimento que compreende uma tal cobertura de ventilador e método para fabricação de uma cobertura de ventilador

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WO2004087223A1 (fr) 2004-10-14
DE10314513A1 (de) 2004-10-14

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