WO1991004779A1 - Process for the production of a semi-finished article, and uses of the article thus produced - Google Patents
Process for the production of a semi-finished article, and uses of the article thus produced Download PDFInfo
- Publication number
- WO1991004779A1 WO1991004779A1 PCT/DE1990/000736 DE9000736W WO9104779A1 WO 1991004779 A1 WO1991004779 A1 WO 1991004779A1 DE 9000736 W DE9000736 W DE 9000736W WO 9104779 A1 WO9104779 A1 WO 9104779A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- semi
- finished product
- product according
- channels
- substances
- 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
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B7/00—Moulds; Cores; Mandrels
- B28B7/34—Moulds, cores, or mandrels of special material, e.g. destructible materials
- B28B7/342—Moulds, cores, or mandrels of special material, e.g. destructible materials which are at least partially destroyed, e.g. broken, molten, before demoulding; Moulding surfaces or spaces shaped by, or in, the ground, or sand or soil, whether bound or not; Cores consisting at least mainly of sand or soil, whether bound or not
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/024—Honeycomb
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/18—Composite material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/20—Plastics, e.g. polymers, polyester, polyurethane
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/40—Activated carbon or charcoal
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the invention is based on methods for producing semi-finished products with a multiplicity of channels, in particular honeycomb bodies, preferably at least in one plane.
- honeycomb bodies are used, for example, as a catalyst or catalyst body in ceramic or metallic form.
- a known method of producing ceramic honeycomb bodies is to extrude and subsequently sinter the inorganic slurries which may contain organic substances.
- the achievable wall thickness downwards and the free cross-sectional area upwards and thus the process engineering use of the honeycomb body are limited.
- Honeycomb bodies for exhaust gas catalytic converters for motor vehicles are therefore also made from metallic material, metal sheets being rolled, then preformed, for example by pleating, and finally wound into the final honeycomb body.
- honeycomb bodies have smaller wall thicknesses and larger free-cut areas than ceramic honeycomb bodies; nevertheless, no free cross-sectional areas of more than 80% can be achieved even with metallic honeycomb bodies.
- a further disadvantage of metallic honeycomb bodies is that it may be necessary to connect the layers which are stacked or wound on one another, for example by soldering. This is not only complex to manufacture, but also leads to greater susceptibility to faults.
- the invention is therefore based on the object of specifying a method for producing semifinished products with a multiplicity, preferably at least in one plane, of parallel channels, in particular honeycomb bodies, which makes it possible to increase the free-sectional area of the semifinished product to over 80% or the wall thickness of the honeycomb body extend below 0.1 mm.
- the method steps specified in claim 1 make it possible to produce a honeycomb body of almost any final shape from any, in particular almost arbitrarily thin, flat preform.
- foils, spinning tiles, trades, knitted fabrics, Knitted fabrics, woven fabrics, injection molding, extrudate, film casting serve as preform.
- the stacked planar preforms can be connected in particular by gluing, sewing, stitching, perforating and printing. The connection can be punctiform, linear or flat.
- the channels formed in this way can in particular be triangular, square, hexagonal or round in cross section.
- the individual layers can be sinusoidal.
- the individual layers can be glued either with a suitable adhesive or with the starting material itself in liquid form.
- the process according to the invention makes it possible to produce honeycomb bodies with very large free-sectional areas and very thin walls, namely from up to 97% free-sectional area and wall thicknesses down to 0.005 mm, while in the case of honeycomb bodies produced by known processes the wall thickness is more than 0.1 mm is. Also important is the large surface area that can be achieved per cubature, which is available as a contact and reaction surface. Up to 1000 channels can be accommodated per square centimeter of inflow area.
- the preform is produced from skin-forming, flowable starting materials which have been shaped or poured over a large area, in particular as a film, and then dried.
- This enables particularly thin preforms are provided, with additives which are required in the later semi-finished product being able to be added to the starting materials prior to the sheet-like shaping.
- such metal-forming starting materials can also be organic metal compounds, organic rare earth compounds, in each case in particular as polymers, metal gels, metal sol gels or other skin-forming substances which contain the substances later required in the semifinished product. It is important that the dried preform remains plastically deformable, for example due to the long molecular chains in the case of polymers.
- inorganic substances such as metals, oxidic and non-oxide ceramics, preferably in a floury form, can be added as additives to the skin-forming starting materials.
- substances required in the later semifinished product can be introduced particularly advantageously, namely in a suspension.
- non-skin-forming substances can also be shaped into a very thin preform.
- the preform according to the invention is in particular manufactured without water.
- Such a green sliver is hydrophobic and has gas separation properties.
- the addition of hygroscopic substances such as "zeolite” can form a hygroscopic green shard which can also have gas separation properties.
- threads and yarns are used for the production of the preform and a semi-finished product is knitted, woven or knitted directly from the preform.
- a semi-finished product with a large number of channels can also be produced, which has a free cross-sectional area of over 80%.
- the dried and expanded basic form is treated with sensitive and / or latent thermal energy in an oxidizing or reducing atmosphere until the material releases the volatile components into the metallic state or into an oxidic or non-oxidized oxide ceramics is converted.
- This thermal treatment of the basic shape produces a ceramic or metallic honeycomb body with extremely thin walls and an extremely large free-sectional area.
- a stable and heat-resistant body is produced which can be used in particular as an exhaust gas catalytic converter in motor vehicles.
- the way to the metallic or ceramic body is chosen by the type of thermal treatment and the treatment atmosphere, while the material of the end product is predetermined by the composition of the starting materials and partly also by the treatment atmosphere.
- a honeycomb body formed from metal silicon by thermal latent En * - ⁇ ie in a reducing atmosphere.
- a ceramic silicon oxide honeycomb body is formed in an oxidizing atmosphere.
- the dried basic form is first converted into the metallic state in a reducing atmosphere with sensitive and / or latent thermal energy and only expanded thereafter. As a result, the volume of the body to be thermally treated is advantageously kept small.
- the inventive method can also be applied to ceramic film produced according to the known slip film casting process, in that the slip casting is enclosed in a still moist and deformable state between plane plastic films or fabrics, several such sandwich layers are placed on top of one another and connected along preferred lines , then the slip casting is preferably dehumidified and fixed by microwave treatment and finally the plastic film is evaporated and decomposed in the firing process, the slip casting being sintered into ceramic or metal.
- the slip casting can also be applied to structured foils in order to give the sintered honeycomb body a certain surface structure.
- connection of the individual layers to one another can also be brought about in that the intermediate foils are perforated, for example, or only foil strips are interposed. be placed so that the slip casting is connected at these points and thereby also the honeycomb body obtained during sintering.
- An advantageous use of the semifinished product according to the invention is its use as an absorber for gaseous or aerosol substances, in particular pollutants such as HC1, HF, S0 X , CO x , NO ⁇ , NH X and amalgam.
- the starting materials for example the suspension, a honeycomb body is obtained, through the channels of which the substances to be absorbed are passed and bound there in solid form.
- the suspension from which the preform is produced can contain magnesium oxide, so that the honeycomb body formed therefrom also contains magnesium oxide as green shards, or a ceramic sintered body made of magnesium oxide is obtained by thermal treatment.
- Gaseous HCl for example, can be introduced into this honeycomb body, which is absorbed there and collected in the form of magnesium chloride.
- a ceramic sintered body made of magnesium oxide can, however, also be obtained by using magnesium alcoholate as a starting material for the preform and thermally treating the honeycomb body in an oxidizing atmosphere. The same applies to other starting materials such as Al, Ca, etc.
- the gaseous or aerosol materials are absorbent materials according to another advantageous embodiment of the Erfin dung applied to the Ha ozeug * r introduced into the channels of the semifinished product and ablative there by ⁇ fluidize the substances to be absorbed.
- the honeycomb body serves as a carrier for the absorbent substances, which are easily accessible by being applied to the honeycomb body, so that a large reaction surface is available.
- the honeycomb body prevents the fluidized absorbent from accumulating on the outer walls of a container that would otherwise be used.
- the absorbent material may accumulate on the channel walls, but the large reaction surface is largely retained.
- the pollutants collected as a saturated or enriched reaction product become ineluctable with water glass or with protein or protein waste or foams in connection with magnesium oxide and / or calcium oxide and / or their hydroxides and / or their carbonates tied. In this way, the pollutants can be made safe for storage.
- the semifinished product according to the invention is used for gas humidification and / or dehumidification, in that the starting materials of the semifinished product are known hygroscopic materials such as magnesium perchlorate, phosphorus pentoxide, silicate, zeolite, aluminosilicate, carbonate carbon , Sodium chloride, polysaccharides and the like.
- the gas to be treated is passed through the channels of the semi-finished product and either releases water or takes up water there.
- the water to be released is due to the hygroscopic substances of the semi-finished product or adsorbed in the semi-finished product.
- gas humidification water adsorbed by the semifinished product is released into the gas.
- Both the large free cross-sectional area and the large reaction surface of the semifinished product according to the invention are again advantageous.
- the hygroscopic materials are preferably added to the starting materials as powder, and if necessary an oxidation can take place in the sintering process.
- the active substance itself in the form of yarn, thread or the like can be used as the starting material for the preform, where necessary an oxidation can take place in the sintering process.
- a metal thread can be woven into the preform and, after the semi-finished product has been produced, sintered to magnesium oxide by thermal treatment in an oxidizing atmosphere.
- the semi-finished product is used in a device for cooling, the semi-finished product having hygroscopic properties and serving as a reservoir for water.
- the water stored in the semifinished product is evaporated by supplying heat, preferably by microwaves, and when a predetermined pressure is reached it is fed via a throttle to a relaxation space, as a result of which it is cooled. After pressure equalization between the relaxation space and the semi-finished product, the water is transported back into the semi-finished product by the hygroscopic effect. Now the water can be evaporated again. Due to the large reaction surface A large evaporation rate of the semi-finished product according to the invention can be achieved, in particular when using microwaves for the supply of heat. This makes such a device for refrigeration particularly economical.
- a heat pipe tube can also be used instead of microwaves. During throttle relaxation, the water can be cooled down to such an extent that it freezes over.
- the semi-finished product according to the invention serves as a static mixer in a hermetically sealed water desalination plant.
- a water desalination plant air circulating in a quasi-adiabatic wash is moistened by salt or brackish water and then dehumidified in a heat exchanger which is cooled on the other hand by the salt or brackish water.
- the resulting distillate is collected as process water.
- the circulation of the air is preferably caused by its humidification and dehumidification. This saves fans that are otherwise required.
- the promotion of salt or brackish water can be advantageous by heating caused expansion can be effected, wherein the heating can be carried out by solar energy, for example by a solar collector. Funding according to the expansion principle also has the advantage that suspended and turbid substances contained in the water can be sedimented.
- the semifinished product is used as a filter, beispielswei ⁇ se as slag melt filter in the 'cottage industry.
- the semi-finished product according to the invention has the advantage that it is heat-resistant and that the required pore size of the filter can be predetermined by the manufacturing process.
- the semi-finished product is used for the selective material separation of gases and / or liquids.
- the semifinished product according to the invention has excellent selective gas separation properties both as a Greenscherr ⁇ n and as a sintered body.
- a gas or liquid separation layer By mutually closing the channels of the semifinished product, a gas or liquid separation layer (Membra: extremely large surface area) is made available.
- These properties of the semifinished product according to the invention can also be used for enriching gas fractions in a gas mixture, in particular of O2 or N2 in air.
- the semifinished product serves as a gas store.
- Such a honeycomb body can be used in particular for storing oxygen and / or carbon dioxide, in that the honeycomb body consists of barium or barium oxide or these are applied to the honeycomb body, preferably in an engobe. Again, the large reaction surface and the large cross-sectional area of such honeycomb bodies are particularly advantageous.
- Such a honeycomb body loaded with oxygen can advantageously serve as an oxygen source in a wide variety of fields of application, for example in oxygen therapy or for the oxidation of the reaction products of suspension dryers.
- such a honeycomb body can be used as a solid hydride storage, in that it consists of magnesium and / or titanium and / or iron or these are applied to the honeycomb body, preferably in an engobe.
- the above-mentioned advantages of the large reaction and free cross-sectional area also apply here. This also gives a particularly large storage capacity per volume, and quick and safe loading and unloading of the solid hydride storage.
- the semifinished product according to the invention serves as a catalyst for the selective and non-selective catalytic treatment of a gas stream, in that the semifinished product made of catalytically active substances such as anatase, iron oxide, tungsten trioxide, Cobalt oxide, vanadium pentoxi, copper oxide, chromium oxide, Spi ⁇ nell, oxides of rare earths and the gas stream is passed through the channels of the semi-finished product.
- catalytically active substances such as anatase, iron oxide, tungsten trioxide, Cobalt oxide, vanadium pentoxi, copper oxide, chromium oxide, Spi ⁇ nell, oxides of rare earths and the gas stream is passed through the channels of the semi-finished product.
- the large achievable free cross-sectional area and the large reaction surface are also particularly advantageous here.
- the semi-finished product serves as a structural component. Due to the extremely thin achievable wall thicknesses, the semi-finished product according to the invention provides a very stable structural component of low weight which can be used, for example, in aircraft construction. As a result of the storage properties which exist with the corresponding starting material, this component can simultaneously be used as a solid hydride storage, for example in aircraft or motor vehicles, as a fuel source.
- the semifinished product according to the invention is used in liquid storage devices.
- the movement of the liquid in the memory is advantageously restricted, as a result of which unfavorable fluctuations in the weight distribution by moving the liquid gas back and forth are avoided. This is important, for example, in the case of fuel tanks in aircraft.
- the semifinished product according to the invention serves as a spacer ring for excess quantity. etched catalyst body.
- the desired shape of the spacer ring is achieved in that strip-shaped semi-finished product is bent around a kiln furniture.
- the strip-shaped semi-finished product is preferably deformed in a wave-like or zigzag shape by pleating or when expanding, so that the semi-finished product is flexible in the longitudinal direction.
- This configuration has the advantage that stresses occurring during sintering of the spacer ring do not lead to the spacer ring being destroyed.
- the kiln furniture provides dimensional stability to contraction during sintering and the wave or zigzag shape gives flexibility when expanding the spacer ring during sintering.
- a single-layer, unexpanded green shard can also be used as the starting material, which is brought into the wave or zigzag shape, for example, by pleating.
- the semi-finished product is used as a silencer, optionally combined with an exhaust gas cleaning function.
- the honeycomb body can either be inserted into the exhaust gas path such that the exhaust gas flows through the channels, or it can be used as a wall coating in the exhaust gas path, the channels of the semi-finished product running perpendicular to the outer wall.
- an exhaust gas purification function can be maintained at the same time.
- the semifinished product contains calcium triphosphate (apatite) and a protein which is compatible with an application site, in particular osteopoietin as a bone replacement and restorative.
- apatite calcium triphosphate
- osteopoietin as a bone replacement and restorative.
- This embodiment of the invention can advantageously be used for medical purposes.
- the well-known property of osteopoetin is used to have a bone-forming effect.
- Calcium triphosphate corresponds to the natural bone material, so that it is particularly well tolerated and a seamless bone replacement made of uniform material is possible, combined with high stability due to the fine channel structure of up to 1000 channels per square centimeter.
- the semifinished product according to the invention serves as a fire seal with smoke seal by means of suspension sealing.
- a honeycomb body according to the invention is used as an insert for the fire closure, suspension, for example, being contained in glass, which is released when a limit temperature is reached by destroying the glass and penetrates into the honeycomb body.
- the suspension is solidified by the heat introduced by the smoke closes the channels of the honeycomb body.
- the semifinished product according to the invention is used in a device with a rotating disk-shaped honeycomb body, the sectors of which are alternately exposed to different media flows in terms of process technology.
- a device with a rotating disk-shaped honeycomb body the sectors of which are alternately exposed to different media flows in terms of process technology.
- Such devices are used for example in gas humidification and / or dehumidification systems, in absorption devices, as catalysts or heat exchangers. Due to the rotation of the honeycomb body, segments of the honeycomb body are alternately exposed to different media flows, for example hot and cold air in heat exchangers of air conditioning systems.
- Such honeycomb bodies are usually equipped with an inner drive and inner bearing, which, according to a further advantageous embodiment of the invention, can be replaced by an outer drive and preferably also an outer bearing of the honeycomb body. This has the advantage that the drive and bearing are not possibly exposed to aggressive gas flows which could destroy them.
- the honeycomb body disk is permanently installed, while the inflow and outflow hoods can be rotated relative to the different media flows.
- the semi-finished product according to the invention is used in an air conditioning and conditioning system.
- the various properties of the honeycomb body can be used advantageously individually or in combination, for example catalytic properties and filter or gas separation properties for cleaning solvent-containing exhaust air, adsorption and heat exchange properties in air conditioning systems, etc.
- the invention Semi-finished products in gas processing plants are used to cool gases by dehumidification, which eliminates the need for unsightly cooling towers.
- the semi-finished product is used as tableware or sanitary ware.
- Such dishes or ceramics can be produced from the preform stacked to form the basic shape by deep drawing, it being possible for the basic shape to be expanded in the same operation or with the same tool.
- deep-drawn ceramic vessels such as plates, cups, as well as deep-drawn wash basins, bathtubs, can advantageously be produced.
- the basic shape can be expanded, for example, by using a vacuum.
- the semi-finished product is sintered to a ceramic body, as described above.
- the semi-finished product is used as an electrode in electrolysis devices or in a fireplace insert such as an accumulator or battery. This configuration has the advantage that the electrode has an extremely large reaction surface, which also brings about good heat dissipation.
- the semifinished product is formed from a photo semiconductor such as TiO 2, gallium or germanium.
- a photo semiconductor such as TiO 2, gallium or germanium.
- the semifinished product consists of inorganic, preferably ceramic, translucent or transparent material and is used as a heat radiation absorber in that the semifinished product is arranged on a surface plate which is darkened on the surface or throughout, preferably also made of ceramic material .
- heat radiation absorbers which are based on the principle of polar bear fur, are known per se. However, these are not heat-resistant or not weatherproof, since they are either made of plastic or made of glass. Due to the honeycomb body made of ceramic material according to the invention, however, such a heat radiation absorber is heat-resistant, weatherproof and comparatively light.
- the dark, in particular black, base area provides high heat absorption, while the channels of the honeycomb body reduce the re-radiation of the absorbed heat.
- the transparency of the ceramic material enables beam absorption at any angle of incidence.
- the dark base plate replaces the skin of the polar bear, while the honeycomb body replaces the hair of the polar bear fur.
- Such a heat radiation absorber can advantageously be used as a focus receiver in solar energy systems, since it is heat-resistant and therefore does not have to be cooled. It can therefore also be used for direct oil refining in the focus receiver of a solar energy system.
- the use of non-oxide ceramics is particularly advantageous since it has a particularly high heat resistance.
- Such a heat radiation absorber can advantageously also be operated in combination with a heat engine.
- a heat engine can be, for example, a Stirling engine that is heated directly or indirectly, or a steam turbine or other steam-operated machine, the steam being generated in the focus receiver or a heat transfer medium being heated, which generates steam elsewhere.
- a heat radiation absorber is used as the facade cladding of buildings.
- the heat radiation absorber is preferably used at the same time as thermal insulation and for heat energy generation.
- such a heat radiation absorber is installed transversely to the facade of a building.
- this is used exclusively for heat energy generation, for example by extending the base plate and / or the honeycomb body into the interior of the building, where they serve as a heating element, for example a hotplate.
- this embodiment can also be used for other heat energy generation.
- such a heat radiation absorber is used for heat insulation, in that the semifinished product is arranged between two sheets which are colored dark on the surface or throughout.
- the honeycomb body takes the place of the otherwise usual mineral wool, which is physiologically questionable.
- the honeycomb structure provides not only the insulator effect but also a high mechanical strength, especially if the channels of the semi-finished product run perpendicular to the dark colored plates.
- the thermal insulation is based on the high reflection in the channels of the semi-finished product, which can be increased further by the fact that, like the inside of the base plates, this is combined with a layer reflecting heat radiation. are seen. In this way, such thermal insulation is also particularly suitable for use as a heat shield in spacecraft, where particularly high mechanical stability is required.
- the semifinished product according to the invention serves as a solid hydride storage in a cycle with metal hydrides of different formation and decomposition temperatures, also in connection with a heat engine.
- hydrogen is expelled from a metal hydride storage by heating and fed to a second solid hydride storage which binds the hydrogen.
- the solid hydride storage at a high formation and decomposition temperature for example magnesium honeycomb body, is preferably heated in connection with an inventive heat radiation absorber, in particular by solar energy, and the hydrogen is driven off.
- This hydrogen is fed to a second solid hydride storage with a low formation and decomposition temperature, for example titanium iron honeycomb bodies, where it is in turn bound.
- the hydrogen stored therein can already be driven off at a low temperature, for example by waste water heat, and can be returned to the solid hydride storage at a high formation temperature.
- the heat energy released during adsorption can either be supplied to heat engines or used directly as heating energy.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
Description
VERFAHREN ZUR HERSTELLUNG EINES HALBZEUGS UND VΕRWENDUNGEN DES HALBZEUGSMETHOD FOR PRODUCING A SEMI-PRODUCT AND USE OF SEMI-PRODUCT
Die Erfindung geht aus von Verfahren zur Herstellung von Halbzeugen mit einer Vielzahl bevorzugt zumindest in einer Ebene paralleler Kanäle, insbesondere Wabenkörper.The invention is based on methods for producing semi-finished products with a multiplicity of channels, in particular honeycomb bodies, preferably at least in one plane.
Derartige Halbzeuge und insbesondere Wabenkörper werden beispielsweise als Katalysator oder Katalysatorkörper in keramischer oder metallischer Form verwendet. Ein bekann¬ tes Verfahren, keramische Wabenkörper herzustellen, be¬ steht darin, eventuell mit organischen Stoffen versetzten anorganischen Schlicker zu extrudieren und anschließend zu sintern. Bei diesem Verfahren sind der erzielbaren Wand¬ dicke nach unten und der Freiquerschnittsfläche nach oben und somit der verfahrenstechnischen Nutzung des Wabenkör¬ pers Grenzen gesetzt. Insbesondere bei Abgaskatalysatoren für Kraftfahrzeuge führt dies zu einem erheblichen Lei¬ stungsverlust. Wabenkörper für Abgaskatalysatoren für Kraftfahrzeuge werden daher auch aus metallischem Werkstoff hergestellt, wobei Metallbleche gewalzt, anschließend beispielsweise durch Plissieren vorgeformt und schließlich zum endgülti¬ gen Wabenkörper gewickelt werden. Diese Wabenkörper weisen zwar geringere Wanddicken und größere Freiquerschnittsflä- chen auf als keramische Wabenkörper; trotzdem sind aber auch mit metallischen Wabenkörpern keine Freiquerschnitts- flächen von mehr als 80% erzielbar. Ein weiterer Nachteil metallischer Wabenkörper besteht darin, daß es unter Um¬ ständen notwendig ist, die übereinandergeschichteten oder gewickelten Lagen beispielsweise durch Löten miteinander zu verbinden. Dies ist nicht nur aufwendig in der Herstel¬ lung, sondern führt auch zu größerer Störanfälligkeit.Such semi-finished products and in particular honeycomb bodies are used, for example, as a catalyst or catalyst body in ceramic or metallic form. A known method of producing ceramic honeycomb bodies is to extrude and subsequently sinter the inorganic slurries which may contain organic substances. In this method, the achievable wall thickness downwards and the free cross-sectional area upwards and thus the process engineering use of the honeycomb body are limited. In particular in the case of exhaust gas catalysts for motor vehicles, this leads to a considerable loss in performance. Honeycomb bodies for exhaust gas catalytic converters for motor vehicles are therefore also made from metallic material, metal sheets being rolled, then preformed, for example by pleating, and finally wound into the final honeycomb body. These honeycomb bodies have smaller wall thicknesses and larger free-cut areas than ceramic honeycomb bodies; nevertheless, no free cross-sectional areas of more than 80% can be achieved even with metallic honeycomb bodies. A further disadvantage of metallic honeycomb bodies is that it may be necessary to connect the layers which are stacked or wound on one another, for example by soldering. This is not only complex to manufacture, but also leads to greater susceptibility to faults.
Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfah¬ ren zur Herstellung von Halbzeugen mit einer Vielzahl bevorzugt zumindest in einer Ebene paralleler Kanäle, insbesondere Wabenkörper, anzugeben, das es ermöglicht, die Freiquerschnittsfläche des Halbzeugs auf über 80% bzw. die Wanddicke des Wabenkörpers unter 0,1 mm zu erstrecken.The invention is therefore based on the object of specifying a method for producing semifinished products with a multiplicity, preferably at least in one plane, of parallel channels, in particular honeycomb bodies, which makes it possible to increase the free-sectional area of the semifinished product to over 80% or the wall thickness of the honeycomb body extend below 0.1 mm.
Diese Aufgabe wird durch das erfindungsgemäße Verfahren nach Anspruch 1 gelöst.This object is achieved by the inventive method according to claim 1.
Durch die in Anspruch 1 angegegebenen Verfahrensschritte ist es möglich, aus einer beliebigen, insbesondere nahezu beliebig dünnen flächenhaften Vorform einen Wabenkörper nahezu beliebiger Endform herzustellen. Auf diese Weise können insbesondere Folien, Spinnfliese, Gewerke, Gewirke, Gestricke, Gewebe, Spritzguß, Extrudat, Folienguß als Vor¬ form dienen. Die Verbindung der gestapelten flächenhaften Vorformen kann insbesondere durch Verkleben, Nähen, Hef¬ ten, Perforieren und Bedrucken erfolgen. Die Verbindung kann hierbei sowohl punktuell, linienhaft als auch flächig sein. Die dadurch gebildeten Kanäle können im Querschnitt insbesondere dreieckig, viereckig, sechseckig oder rund gestaltet sein. Beispielsweise können die einzelnen Lagen sinusartig gewellt sein. Das Verkleben der einzelnen Lagen kann entweder durch einen geeigneten Klebstoff, oder aber durch den Ausgangsstoff selbst in flüssiger Form erfolgen.The method steps specified in claim 1 make it possible to produce a honeycomb body of almost any final shape from any, in particular almost arbitrarily thin, flat preform. In this way, foils, spinning tiles, trades, knitted fabrics, Knitted fabrics, woven fabrics, injection molding, extrudate, film casting serve as preform. The stacked planar preforms can be connected in particular by gluing, sewing, stitching, perforating and printing. The connection can be punctiform, linear or flat. The channels formed in this way can in particular be triangular, square, hexagonal or round in cross section. For example, the individual layers can be sinusoidal. The individual layers can be glued either with a suitable adhesive or with the starting material itself in liquid form.
Durch das erfindungsgemäße Verfahren sind Wabenkörper mit sehr großen Freiquerschnittsflächen und sehr dünnen Wandun¬ gen herstellbar, nämlich von bis zu 97% Freiquerschnitts¬ fläche und Wanddicken bis zu 0,005 mm hinab, während bei nach bekannten Verfahren hergestellten Wabenkörpern die Wandstärke mehr als 0,1 mm beträgt. Bedeutsam ist auch die dadurch erzielbare große Oberfläche pro Kubatur, die als Kontakt- und Reaktionsfläche zur Verfügung steht. Es las¬ sen sich bis zu 1000 Kanäle pro Quadratzentimeter Anström¬ fläche unterbringen.The process according to the invention makes it possible to produce honeycomb bodies with very large free-sectional areas and very thin walls, namely from up to 97% free-sectional area and wall thicknesses down to 0.005 mm, while in the case of honeycomb bodies produced by known processes the wall thickness is more than 0.1 mm is. Also important is the large surface area that can be achieved per cubature, which is available as a contact and reaction surface. Up to 1000 channels can be accommodated per square centimeter of inflow area.
Nach einer vorteilhaften Ausgestaltung der Erfindung wird die Vorform aus hautbildenden fließfähigen Ausgangsstoffen hergestellt, welche flächenhaft, insbesondere als Folie, ausgeformt oder ausgegossen und anschließend getrocknet wurden. Hierdurch können besonders dünne Vorformen herge- stellt werden, wobei den Ausgangsstoffen vor dem flächen¬ haften Ausformen Zusatzstoffe hinzugefügt werden können, die in dem späteren Halbzeug benötigt werden.According to an advantageous embodiment of the invention, the preform is produced from skin-forming, flowable starting materials which have been shaped or poured over a large area, in particular as a film, and then dried. This enables particularly thin preforms are provided, with additives which are required in the later semi-finished product being able to be added to the starting materials prior to the sheet-like shaping.
Als derartige hautbildende Ausgangsstoffe können nach einer weiteren vorteilhaften Ausgestaltung der Erfindung auch organische Metallverbindungen, organische Seltenerden¬ verbindungen, jeweils insbesondere als Polymere, Metallge¬ le, Metallsolgele oder sonstige hautbildende Stoffe die¬ nen, welche die später im Halbzeug benötigten Stoffe ent¬ halten. Wichtig ist, daß die getrocknete Vorform plastisch verformbar bleibt, bei Polymeren beispielsweise aufgrund der langen Molekülketten.According to a further advantageous embodiment of the invention, such metal-forming starting materials can also be organic metal compounds, organic rare earth compounds, in each case in particular as polymers, metal gels, metal sol gels or other skin-forming substances which contain the substances later required in the semifinished product. It is important that the dried preform remains plastically deformable, for example due to the long molecular chains in the case of polymers.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung können als Zusatzstoffe zu den hautbildenden Ausgangs¬ stoffen anorganische Stoffe wie Metalle, oxidische und nichtoxidische Keramik, bevorzugt in mehliger Form, zugege¬ ben werden. Auf diese Weise können besonders vorteilhaft, nämlich in einer Suspension, im späteren Halbzeug benötig¬ te Stoffe eingebracht werden. Der Vorteil liegt darin, daß so auch nichthautbildende Stoffe zu einer sehr dünnen Vorform ausformbar sind. Die erfindungsgemäße Vorform wird insbesondere wasserfrei hergestellt. Ein solcher Grünscher¬ ben ist hydrophob und weist Gastrenneigenschaften auf. Durch den .Zusatz hygroskopischer Stoffe wie "Zeolith" kann ein hygroskopischer Grünscherben gebildet werden, der ebenfalls Gastrenneigenschaften aufweisen kann. Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung werden für die Herstellung der Vorform Fäden und Garne verwendet und aus der Vorform unmittelbar ein Halb¬ zeug gemäß Anspruch 1 gewirkt, gewoben oder gestrickt. Hierdurch kann auch ein Halbzeug mit einer Vielzahl von Kanälen hergestellt werden, welches eine Freiquerschnitts¬ fläche von über 80% aufweist.According to a further advantageous embodiment of the invention, inorganic substances such as metals, oxidic and non-oxide ceramics, preferably in a floury form, can be added as additives to the skin-forming starting materials. In this way, substances required in the later semifinished product can be introduced particularly advantageously, namely in a suspension. The advantage is that non-skin-forming substances can also be shaped into a very thin preform. The preform according to the invention is in particular manufactured without water. Such a green sliver is hydrophobic and has gas separation properties. The addition of hygroscopic substances such as "zeolite" can form a hygroscopic green shard which can also have gas separation properties. According to a further advantageous embodiment of the invention, threads and yarns are used for the production of the preform and a semi-finished product is knitted, woven or knitted directly from the preform. In this way, a semi-finished product with a large number of channels can also be produced, which has a free cross-sectional area of over 80%.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung wird die getrocknete und aufgeweitete Grundform mit sensibler und/oder latenter thermischer Energie in oxidie- render oder reduzierender Atmosphäre behandelt bis der Werkstoff unter Freigabe der flüchtigeh Anteile in den metallischen Zustand oder zu einer oxidischen oder nichto- xidischen Keramik umgewandelt wird. Durch diese thermische Behandlung der Grund orm wird ein keramischer oder metalli¬ scher Wabenkörper erzeugt, mit äußerst dünnen Wandungen und extrem großer Freiquerschnittsfläche. Es wird ein stabiler und hitzebeständiger Körper erzeugt, der insbeson¬ dere als Abgaskatalysator in Kraftfahrzeugen einsetzbar ist. Der Weg zum metallischen oder keramischen Körper wird durch die Art der thermischen Behandlung und die Behand¬ lungsatmosphäre gewählt, während das Material des Endpro¬ dukts durch die Zusammensetzung der Ausgangsstoffe und zum Teil auch durch die Behandlungsatmosphäre vorbestimmt ist. So kann aus einer aus Siliziumalkoholat hergestellten Vorform ein Wabenkörper aus metallischem Silizium gebildet werden durch latente thermische En*- γie in reduzierender Atmosphäre. In oxidierender Atmosp ire wird dagegen ein keramischer Siliziumoxid-Wabenkörper gebildet. Nach einer anderen vorteilhaften Ausgestaltung der Erfin¬ dung wird die getrocknete Grundform zunächst in einer redu¬ zierenden Atmosphäre mit sensibler und/oder latenter ther¬ mischer Energie in den metallischen Zustand umgewandelt und erst im Anschluß daran aufgeweitet. Dadurch wird das Volumen des thermisch zu behandelnden Körpers vorteilhafterweise klein gehalten.According to a further advantageous embodiment of the invention, the dried and expanded basic form is treated with sensitive and / or latent thermal energy in an oxidizing or reducing atmosphere until the material releases the volatile components into the metallic state or into an oxidic or non-oxidized oxide ceramics is converted. This thermal treatment of the basic shape produces a ceramic or metallic honeycomb body with extremely thin walls and an extremely large free-sectional area. A stable and heat-resistant body is produced which can be used in particular as an exhaust gas catalytic converter in motor vehicles. The way to the metallic or ceramic body is chosen by the type of thermal treatment and the treatment atmosphere, while the material of the end product is predetermined by the composition of the starting materials and partly also by the treatment atmosphere. Thus, from a preform made of silicon alkoxide, a honeycomb body formed from metal silicon by thermal latent En * - γie in a reducing atmosphere. In contrast, a ceramic silicon oxide honeycomb body is formed in an oxidizing atmosphere. According to another advantageous embodiment of the invention, the dried basic form is first converted into the metallic state in a reducing atmosphere with sensitive and / or latent thermal energy and only expanded thereafter. As a result, the volume of the body to be thermally treated is advantageously kept small.
Das erfinderische Verfahren kann auch auf nach dem an sich bekannten Schlickerfoliengußverfahren hergestellte Keramik¬ folie angewandt werden, indem der Schlickerguß in gerade noch feuchtem und verformbarem Zustand zwischen planebenen Plastikfolien oder Gewebe eingeschlossen wird, mehrere solcher Sandwichlagen aufeinandergelegt und entlang bevor¬ zugt paralleler Linien verbunden werden, sodann der Schlickerguß vorzugsweise durch Mikrowellenbehandlung entfeuchtet und fixiert wird und schließlich die Plastikfo¬ lie im Brennverfahren verdampft und zersetzt wird, wobei der Schlickerguß zu Keramik oder Metall gesintert wird.The inventive method can also be applied to ceramic film produced according to the known slip film casting process, in that the slip casting is enclosed in a still moist and deformable state between plane plastic films or fabrics, several such sandwich layers are placed on top of one another and connected along preferred lines , then the slip casting is preferably dehumidified and fixed by microwave treatment and finally the plastic film is evaporated and decomposed in the firing process, the slip casting being sintered into ceramic or metal.
Der Schlickerguß kann auch auf strukturierte Folien aufge¬ bracht werden, um dem gesinterten Wabenkörper eine bestimm¬ te Oberflächenstruktur zu geben.The slip casting can also be applied to structured foils in order to give the sintered honeycomb body a certain surface structure.
Die Verbindung der einzelnen Lagen untereinander kann auch dadurch bewirkt werden, daß die Zwischenfolien beispiels¬ weise perforiert sind oder nur Folienstreifen zwischenge- legt werden, so daß der Schlickerguß an diesen Stellen verbunden ist und dadurch auch der beim Sintern erhaltene Wabenkörper.The connection of the individual layers to one another can also be brought about in that the intermediate foils are perforated, for example, or only foil strips are interposed. be placed so that the slip casting is connected at these points and thereby also the honeycomb body obtained during sintering.
Eine vorteilhafte Verwendung des erfindungsgemäßen Halb¬ zeugs besteht in seiner Verwendung als Absorber für gasför¬ mige oder aerosole Stoffe, insbesondere Schadstoffe wie HC1, HF, S0X, COx, NOχ, NHX und Amalgam. Durch entsprechen¬ de Wahl der Ausgangsstoffe, beispielsweise der Suspension, wird ein Wabenkörper erhalten, durch dessen Kanäle die zu absorbierenden Stoffe geleitet und dort in fester Form gebunden werden. So kann beispielsweise die Suspension, aus der die Vorform hergestellt wird, Magnesiumoxid enthal¬ ten, so daß der daraus gebildete Wabenkörper als Grünscher¬ ben ebenfalls Magnesiumoxid enthält oder durch thermische Behandlung ein keramischer Sinterkörper aus Magnesiumoxid erhalten wird. In diesen Wabenkörper kann beispielsweise gasförmiges HCl eingeleitet werden, welches dort absor¬ biert und in Form von Magnesiumchlorid gesammelt wird. Ein keramischer Sinterkörper aus Magnesiumoxid kann aber auch dadurch erhalten werden, daß Magnesiumalkoholat als Aus¬ gangsstoff für die Vorform verwendet wird und der Wabenkör¬ per in oxidierender Atmosphäre thermisch behandelt wird. Entsprechendes gilt für andere Ausgangsstoffe wie AI, Ca, etc.An advantageous use of the semifinished product according to the invention is its use as an absorber for gaseous or aerosol substances, in particular pollutants such as HC1, HF, S0 X , CO x , NOχ, NH X and amalgam. By appropriate choice of the starting materials, for example the suspension, a honeycomb body is obtained, through the channels of which the substances to be absorbed are passed and bound there in solid form. For example, the suspension from which the preform is produced can contain magnesium oxide, so that the honeycomb body formed therefrom also contains magnesium oxide as green shards, or a ceramic sintered body made of magnesium oxide is obtained by thermal treatment. Gaseous HCl, for example, can be introduced into this honeycomb body, which is absorbed there and collected in the form of magnesium chloride. A ceramic sintered body made of magnesium oxide can, however, also be obtained by using magnesium alcoholate as a starting material for the preform and thermally treating the honeycomb body in an oxidizing atmosphere. The same applies to other starting materials such as Al, Ca, etc.
Nach einer anderen vorteilhaften Ausgestaltung der Erfin¬ dung werden die die gasförmigen oder aerosolen Stoffe absorbierenden Stoffe auf das Ha ozeug aufgebracht * r in die Kanäle des Halbzeugs eingebracht und dort durch ^abla- sen der zu absorbierenden Stoffe fluidisiert. Im ersten Fall dient der Wabenkörper als Träger der absorbierenden Stoffe, die durch Aufbringen auf den Wabenkörper gut zugänglich sind, so daß eine große Reaktionsoberfläche zur Verfügung steht. Im zweiten Fall verhindert der Wabenkör¬ per das Ansammeln des fluidisierten Absorbens an den Außen¬ wänden eines sonst zu verwendenden Behälters. Der absorbie¬ rende Stoff lagert sich gegebenenfalls an den Kanalwänden an, wobei die große Reaktionsoberfläche aber weitgehend erhalten bleibt.The gaseous or aerosol materials are absorbent materials according to another advantageous embodiment of the Erfin dung applied to the Ha ozeug * r introduced into the channels of the semifinished product and ablative there by ^ fluidize the substances to be absorbed. In the first case, the honeycomb body serves as a carrier for the absorbent substances, which are easily accessible by being applied to the honeycomb body, so that a large reaction surface is available. In the second case, the honeycomb body prevents the fluidized absorbent from accumulating on the outer walls of a container that would otherwise be used. The absorbent material may accumulate on the channel walls, but the large reaction surface is largely retained.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung werden die als gesättigtes oder angereichertes Reakti¬ onsprodukt gesammelten Schadstoffe mit Wasserglas oder mit Eiweiß oder Eiweißabfällen oder Föken in Verbindung mit Magnesiumoxid und/oder Kalziumoxid und/oder deren Hydroxi¬ de und/oder deren Karbonate uneluierbar abgebunden. Auf diese Weise können die Schadstoffe gefahrlos lagerbar gemacht werden.According to a further advantageous embodiment of the invention, the pollutants collected as a saturated or enriched reaction product become ineluctable with water glass or with protein or protein waste or foams in connection with magnesium oxide and / or calcium oxide and / or their hydroxides and / or their carbonates tied. In this way, the pollutants can be made safe for storage.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das erfindungsgemäße Halbzeug zur Gasbe- und/o¬ der -entfeuchtung, indem die Ausgangsstoffe des Halbzeugs an sich bekannte hygroskopische Materialen wie Magnesi- umperlchlorat, Phosphorpentoxid, Silikat, Zeolith, Alumosi- likat, Karbonatkohlenstoff, Natriumchlorid, Polysaccharide und dergleichen enthalten. Das zu behandelnde Gas wird durch die Kanäle des Halbzeugs geleitet und gibt dort entweder Wasser ab oder nimmt Wasser auf. Das abzugebende Wasser wird durch die hygroskopischen Stoffe des Halbzeugs bzw. im Halbzeug adsorbiert. Bei der Gasbefeuchtung wird durch das Halbzeug adsorbiertes Wasser an das Gas abgege¬ ben. Hierbei ist wiederum sowohl die große Freiquerschnittsfläche als auch die große Reaktionsoberflä¬ che des erfindungsgemäßen Halbzeugs von Vorteil. Die hy¬ groskopischen Materialien werden den Ausgangsstoffen bevor¬ zugt als Pulver zugegeben, wobei erforderlichenfalls eine Aufoxidation im Sinter" ozeß stattfinden kann.According to a further advantageous embodiment of the invention, the semifinished product according to the invention is used for gas humidification and / or dehumidification, in that the starting materials of the semifinished product are known hygroscopic materials such as magnesium perchlorate, phosphorus pentoxide, silicate, zeolite, aluminosilicate, carbonate carbon , Sodium chloride, polysaccharides and the like. The gas to be treated is passed through the channels of the semi-finished product and either releases water or takes up water there. The water to be released is due to the hygroscopic substances of the semi-finished product or adsorbed in the semi-finished product. During gas humidification, water adsorbed by the semifinished product is released into the gas. Both the large free cross-sectional area and the large reaction surface of the semifinished product according to the invention are again advantageous. The hygroscopic materials are preferably added to the starting materials as powder, and if necessary an oxidation can take place in the sintering process.
Es ist auch möglich, den Wirkstoff selbst in Form von Garn, Faden oder dergleichen als Ausgangsstoff für die Vorform zu verwenden, wobei erforderlichenfalls eine Auf¬ oxidation im Sinterprozeß stattfinden kann. So kann bei¬ spielsweise ein Metallfaden zur Vorform gewoben werden und nach Herstellen des Halbzeugs durch thermische Behandlung in oxidierender Atmosphäre zu Magnesiumoxid gesintert werden.It is also possible to use the active substance itself in the form of yarn, thread or the like as the starting material for the preform, where necessary an oxidation can take place in the sintering process. For example, a metal thread can be woven into the preform and, after the semi-finished product has been produced, sintered to magnesium oxide by thermal treatment in an oxidizing atmosphere.
Nach »er weiteren vorteilhaften Ausgestaltung der Erfin¬ dung w-i-rd das Halbzeug in einer Vorrichtung zur Kälteerzeu¬ gung verwendet, wobei das Halbzeug hygroskopische Eigen¬ schaften aufweist und als Speicher für Wasser dient. Das im Halbzeug gespeicherte Wasser wird durch Wärmezufuhr, bevorzugt durch Mikrowellen, verdampft, bei Erreichen eines vorbestimmten Druckes über eine Drossel einem Ent¬ spannungsraum zugeführt, wodurch dieser abgekühlt wird. Nach Druckausgleich zwischen Entspannungsraum und Halbzeug wird das Wasser durch die hygroskopische Wirkung des Halb¬ zeugs in dieses zurückbefördert. Nun kann das Wasser er¬ neut verdampft werden. Durch die große Reaktionsoberfläche des erfindungsgemäßen Halbzeugs kann, insbesondere bei Verwendung von Mikrowellen zur Wärmezufuhr, eine große Ver¬ dampfungsrate erzielt werden. Hierdurch wird eine derarti¬ ge Vorrichtung zur Kälteerzeugung besonders wirtschaft¬ lich. Anstelle von Mikrowellen kann auch ein Heatpiperohr eingesetzt werden. Das Wasser kann bei der Drosselentspan¬ nung soweit abgekühlt werden, daß es vereist.According to a further advantageous embodiment of the invention, the semi-finished product is used in a device for cooling, the semi-finished product having hygroscopic properties and serving as a reservoir for water. The water stored in the semifinished product is evaporated by supplying heat, preferably by microwaves, and when a predetermined pressure is reached it is fed via a throttle to a relaxation space, as a result of which it is cooled. After pressure equalization between the relaxation space and the semi-finished product, the water is transported back into the semi-finished product by the hygroscopic effect. Now the water can be evaporated again. Due to the large reaction surface A large evaporation rate of the semi-finished product according to the invention can be achieved, in particular when using microwaves for the supply of heat. This makes such a device for refrigeration particularly economical. A heat pipe tube can also be used instead of microwaves. During throttle relaxation, the water can be cooled down to such an extent that it freezes over.
Nach einer vorteilhaften Weiterbildung dieser Merkmale werden mehrere derartige Reaktoren verwendet, die zyklisch ausgetauscht werden können, um jeweils in der Stillstand¬ sphase regeneriert zu werden. Auf diese Weise ist eine ausreichende Kühlkapazität auch ohne kontinuierlichen Betrieb erreichbar.According to an advantageous development of these features, several such reactors are used which can be exchanged cyclically in order to be regenerated in each case in the standstill phase. In this way, sufficient cooling capacity can be achieved even without continuous operation.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das erfindungsgemäße Halbzeug als statischer Mischer in einer hermetisch abgeschlossenen Wasserentsalzungsanlage. Bei einer derartigen Wasserentsalzungsanlage wird in einer quasi adiabatischen Wäsche zirkulierende Luft durch Salz- oder Brackwasser befeuchtet und anschließend in einem Wärmetauscher ent¬ feuchtet, der andererseits durch das Salz- oder Brackwas¬ ser gekühlt wird. Das dabei entstehende Destillat wird als Brauchwasser gesammelt.According to a further advantageous embodiment of the invention, the semi-finished product according to the invention serves as a static mixer in a hermetically sealed water desalination plant. In such a water desalination plant, air circulating in a quasi-adiabatic wash is moistened by salt or brackish water and then dehumidified in a heat exchanger which is cooled on the other hand by the salt or brackish water. The resulting distillate is collected as process water.
Die Zirkulation der Luft wird bevorzugt durch ihre Be- und Entfeuchtung bewirkt. Dadurch werden sonst erforderliche Ventilatoren eingespart. Die Förderung des Salz- oder Brackwassers kann vorteilhaft durch die durch Erwärmung hervorgerufene Expansion bewirkt werden, wobei die Erwär¬ mung durch Sonnenenergie, beispielsweise durch einen Son¬ nenkollektor, vorgenommen werden kann. Die Förderung nach dem Expansionsprinzip hat zudem den Vorteil, daß im Wasser enthaltene Schweb- und Trubstoffe sedimentiert werden können.The circulation of the air is preferably caused by its humidification and dehumidification. This saves fans that are otherwise required. The promotion of salt or brackish water can be advantageous by heating caused expansion can be effected, wherein the heating can be carried out by solar energy, for example by a solar collector. Funding according to the expansion principle also has the advantage that suspended and turbid substances contained in the water can be sedimented.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung wird das Halbzeug als Filter verwendet, beispielswei¬ se als Schlacke-Schmelze-Filter in der ' Hüttenindustrie. Das erfindungsgemäße Halbzeug weist hierbei den Vorteil auf, daß es hitzebeständig ist, und daß die erforderliche Porengröße des Filters durch den Herstellungsprozeß vorbe¬ stimmbar ist.According to a further advantageous embodiment of the dung Erfin the semifinished product is used as a filter, beispielswei¬ se as slag melt filter in the 'cottage industry. The semi-finished product according to the invention has the advantage that it is heat-resistant and that the required pore size of the filter can be predetermined by the manufacturing process.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das Halbzeug für die selektive Stofftremung von Gasen und/oder Flüssigkeiten. Das erfindungsgemäße Halbzeug weist sowohl als Grünscherr^n als auch als Sinter¬ körper hervorragende selektive Gastrenneigenschaften auf. Durch wechselseitiges Verschließen der Kanäle des Halb¬ zeugs wird so eine Gas- oder Flüssigkeitstrennschicht (Membra: äußerst großer Oberfläche zur Verfügung gestellt. Diese Eigenschaften des erfindungsgemäßen Halb¬ zeugs können auch zur Anreicherung von Gasanteilen in einem Gasgemisch verwendet werden, insbesondere von O2 oder N2 in Luft. Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung, die auch für gattungsgemäße Wabenkörper beansprucht wird, dient das Halbzeug als Gasspeicher. Ein derartiger Wabenkörper kann insbesondere zur Speicherung von Sauer¬ stoff und/oder Kohlendioxid verwendet werden, indem der Wabenkörper aus Barium oder Bariumoxid besteht oder diese, bevorzugt in einer Engobe, auf den Wabenkörper aufgebracht sind. Wiederum ist die große Reaktionsoberfläche und die große Freiquerschnittsfläche solcher Wabenkörper besonders vorteilhaft. Ein solcher mit Sauerstoff beladener Wabenkör¬ per kann vorteilhaft als Sauerstoffquelle in den verschie¬ densten Anwendungsgebieten dienen, beispielsweise in der Sauerstofftherapie oder zur Aufoxidation der Reaktionspro¬ dukte von Suspensionstrocknern.According to a further advantageous embodiment of the invention, the semi-finished product is used for the selective material separation of gases and / or liquids. The semifinished product according to the invention has excellent selective gas separation properties both as a Greenscherr ^ n and as a sintered body. By mutually closing the channels of the semifinished product, a gas or liquid separation layer (Membra: extremely large surface area) is made available. These properties of the semifinished product according to the invention can also be used for enriching gas fractions in a gas mixture, in particular of O2 or N2 in air. According to a further advantageous embodiment of the invention, which is also claimed for generic honeycomb bodies, the semifinished product serves as a gas store. Such a honeycomb body can be used in particular for storing oxygen and / or carbon dioxide, in that the honeycomb body consists of barium or barium oxide or these are applied to the honeycomb body, preferably in an engobe. Again, the large reaction surface and the large cross-sectional area of such honeycomb bodies are particularly advantageous. Such a honeycomb body loaded with oxygen can advantageously serve as an oxygen source in a wide variety of fields of application, for example in oxygen therapy or for the oxidation of the reaction products of suspension dryers.
Ebenso kann ein derartiger Wabenkörper als Feststoffhydrid¬ speicher verwendet werden, indem er aus Magnesium und/oder Titan und/oder Eisen besteht oder diese auf den Wabenkör¬ per, bevorzugt in einer Engobe, aufgebracht sind. Auch hier gelten die bereits obengenannten Vorteile der großen Reaktions- und Freiquerschnittsfläche. Hierdurch ist auch eine besonders große Speicherkapazität pro Volumen gegeben sowie eine schnelle und sichere Be- und Entladung des Fest¬ stoffhydridspeichers.Likewise, such a honeycomb body can be used as a solid hydride storage, in that it consists of magnesium and / or titanium and / or iron or these are applied to the honeycomb body, preferably in an engobe. The above-mentioned advantages of the large reaction and free cross-sectional area also apply here. This also gives a particularly large storage capacity per volume, and quick and safe loading and unloading of the solid hydride storage.
Nach einer, weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das erfindungsgemäße Halbzeug als Katalysator für die selektive und nichtselektive katalytische Behand¬ lung eines Gasstroms, indem das Halbzeug aus katalytisch wirksamen Stoffen wie Anatas, Eisenoxid, Wolframtrioxid, Kobaltoxid, Vanadiumpentoxi , Kupferoxid, Chromoxid, Spi¬ nell, Oxiden von Seltenerden besteht und der Gasstrom durch die Kanäle des Halbzeugs geleitet wird. Die große erzielbare Freiquerschnittsfläche und die große Reakti¬ onsoberfläche sind auch hier besonders vorteilhaft.According to a further advantageous embodiment of the invention, the semifinished product according to the invention serves as a catalyst for the selective and non-selective catalytic treatment of a gas stream, in that the semifinished product made of catalytically active substances such as anatase, iron oxide, tungsten trioxide, Cobalt oxide, vanadium pentoxi, copper oxide, chromium oxide, Spi¬ nell, oxides of rare earths and the gas stream is passed through the channels of the semi-finished product. The large achievable free cross-sectional area and the large reaction surface are also particularly advantageous here.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das Halbzeug als strukturelles Bauteil. Durch die äußerst dünnen erzielbaren Wandstärken wird durch das erfindungsgemäße Halbzeug ein sehr stabiles strukturelles Bauteil geringen Gewichts zur Verfügung gestellt, das beispielsweise im Flugzeugbau einsetzbar ist. Durch die bei entsprechendem Ausgangsstoff bestehenden Speichereigen¬ schaften kann dieses Bauteil gleichzeitig als Feststoffhy¬ dridspeicher, beispielsweise in Flugzeugen oder Kraftfahr¬ zeugen, als Brennstoffquelle verwendet werden.According to a further advantageous embodiment of the invention, the semi-finished product serves as a structural component. Due to the extremely thin achievable wall thicknesses, the semi-finished product according to the invention provides a very stable structural component of low weight which can be used, for example, in aircraft construction. As a result of the storage properties which exist with the corresponding starting material, this component can simultaneously be used as a solid hydride storage, for example in aircraft or motor vehicles, as a fuel source.
Nach einer vorteilhaften Weiterbildung dieser Merkmale dient das erfindungsgemäße Halbzeug als Einsatz in Flüssig¬ keitsspeichern. Hierdurch wird die Bewegung der Flüssig¬ keit in dem Speicher vorteilhafterweise eingeschränkt, wodurch ungünstige Schwankungen in der Gewichtsverteilung durch Hin- und Herbewegen des Flüssiggases vermieden wer¬ den. Dies ist beispielsweise bei Brennstofftanks in Flug¬ zeugen wichtig.According to an advantageous development of these features, the semifinished product according to the invention is used in liquid storage devices. As a result, the movement of the liquid in the memory is advantageously restricted, as a result of which unfavorable fluctuations in the weight distribution by moving the liquid gas back and forth are avoided. This is important, for example, in the case of fuel tanks in aircraft.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin- d -ng dient das Tfindungsgemäße Halbzeug als Distanzring für zu Λmmenge. tzte Katalysatorkörper. Die gewünschte Form des Distanzrings wird dabei dadurch erzielt, daß streifenförmiges Halbzeug um ein Brennhilfsmittel gebogen wird. Zuvor wird jedoch das streifenförmige Halbzeug bevor¬ zugt durch Plissieren oder beim Aufweiten wellen- oder zickzackförmig verformt, so daß eine Flexibilität des Halbzeugs in Längsrichtung gegeben ist. Diese Ausgestal¬ tung hat den Vorteil, daß beim Sintern des Distanzringes auftretende Spannungen nicht zu einem Zerstören des Dis¬ tanzrings führen. Durch das Brennhilfsmittel ist Formstabi¬ lität gegenüber Zusammenziehen beim Sintern gegeben und durch die Wellen- oder Zickzackform Flexibilität beim Expandieren des Distanzringes während des Sintern. Hier¬ durch werden sehr paßgenaue Distanzringe fertigbar bei nahezu beliebiger Form des Distanzringes, beispielsweise ovaler oder rechteckiger Freiquerschnittsfläche. Als Aus¬ gangsmaterial kann auch ein einlagiger, nicht aufgeweite¬ ter Grünscherben verwendet werden, der beispielsweise durch Plissieren in die Wellen- oder Zickzackform gebracht wird.According to a further advantageous embodiment of the invention, the semifinished product according to the invention serves as a spacer ring for excess quantity. etched catalyst body. The desired shape of the spacer ring is achieved in that strip-shaped semi-finished product is bent around a kiln furniture. Before this, however, the strip-shaped semi-finished product is preferably deformed in a wave-like or zigzag shape by pleating or when expanding, so that the semi-finished product is flexible in the longitudinal direction. This configuration has the advantage that stresses occurring during sintering of the spacer ring do not lead to the spacer ring being destroyed. The kiln furniture provides dimensional stability to contraction during sintering and the wave or zigzag shape gives flexibility when expanding the spacer ring during sintering. This makes it possible to produce very precisely fitting spacer rings with almost any shape of the spacer ring, for example oval or rectangular free-cut surface. A single-layer, unexpanded green shard can also be used as the starting material, which is brought into the wave or zigzag shape, for example, by pleating.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung wird das Halbzeug als Schalldämpfer verwendet, gegebe¬ nenfalls kombiniert mit Abgasreinigungsfunktion. Der Waben¬ körper kann hierbei entweder so in den Abgasweg eingesetzt werden, daß das Abgas die Kanäle durchströmt, oder aber er kann als Wandbeschichtung im Abgasweg verwendet werden, wobei die Kanäle des Halbzeugs senkrecht zur Außenwand ver¬ laufen. Bei Verwendung von Katalysatormaterial für das Halbzeug kann gleichzeitig eine Abgasreinigungsfunktion er¬ halten werden. Der Vorteil besteht darin, daß beim Durch¬ strömen eine sehr große Freiquerschnittsfläche gegeben ist, woraus ein sehr geringer Staudruck resultiert. Im zweiten Fall ist der Staudruck ebenfalls gering, wobei hier die Schalldämpfung aus der Resonatorwirkung der Kanä¬ le in Verbindung mit der Porosität des Materials resul¬ tiert.According to a further advantageous embodiment of the invention, the semi-finished product is used as a silencer, optionally combined with an exhaust gas cleaning function. The honeycomb body can either be inserted into the exhaust gas path such that the exhaust gas flows through the channels, or it can be used as a wall coating in the exhaust gas path, the channels of the semi-finished product running perpendicular to the outer wall. When using catalyst material for the semi-finished product, an exhaust gas purification function can be maintained at the same time. The advantage is that there is a very large free cross-sectional area when flowing through is what results in a very low back pressure. In the second case, the dynamic pressure is also low, with the sound damping resulting from the resonator effect of the channels in connection with the porosity of the material.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung enthält das Halbzeug Kalziumtriphosphat (Apatit) und ein mit einer Applikationsstelle verträgliches Eiweiß, insbesondere Osteopoetin als Knochenersatz und -aufbaumit- tel. Diese Ausgestaltung der Erfindung kann vorteilhafter¬ weise zu medizinischen Zwecken eingesetzt werden. Hierbei wird die bekannte Eigenschaft von Osteopoetin ausgenutzt, knochenbildend zu wirken. Kalziumtriphosphat entspricht dem natürlichen Knochenmaterial, so daß besonders gute Ver¬ träglichkeit gegeben ist und ein nahtloser Knochenersatz aus einheitlichem Material möglich ist, verbunden mit hoher Stabilität aufgrund der feinen Kanalstruktur von bis zu 1000 Kanälen pro Quadratzentimeter.According to a further advantageous embodiment of the invention, the semifinished product contains calcium triphosphate (apatite) and a protein which is compatible with an application site, in particular osteopoietin as a bone replacement and restorative. This embodiment of the invention can advantageously be used for medical purposes. Here, the well-known property of osteopoetin is used to have a bone-forming effect. Calcium triphosphate corresponds to the natural bone material, so that it is particularly well tolerated and a seamless bone replacement made of uniform material is possible, combined with high stability due to the fine channel structure of up to 1000 channels per square centimeter.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das erfindungsgemäße Halbzeug als Brandabschluß mit Rauchabschluß durch Suspensionsabdichtung. Ein erfin¬ dungsgemäßer Wabenkörper wird als Einsatz für den Brandab¬ schluß verwendet, wobei oberhalb des Wabenkörpers beispielsweise in Glas eingeschlossene Suspension gelagert ist, welche bei Erreichen einer Grenztemperatur durch Zerstörung des Glases freigesetzt wird und in die an le • -»s Wabenkörpers eindringt. Durch die durch den Rauch eingetragene Wärme wird die Suspension verfestigt und verschließt die Kanäle des Wabenkörpers. Diese Ausgestal¬ tung hat den Vorteil, daß ein sicherer Brandabschluß gege¬ ben ist bei gleichzeitigem Rauchabschluß, während vor Freisetzung der Suspension ein Gasdurchtritt durch den Wabenkörper möglich ist, beispielsweise in Klimaanlagen.According to a further advantageous embodiment of the invention, the semifinished product according to the invention serves as a fire seal with smoke seal by means of suspension sealing. A honeycomb body according to the invention is used as an insert for the fire closure, suspension, for example, being contained in glass, which is released when a limit temperature is reached by destroying the glass and penetrates into the honeycomb body. The suspension is solidified by the heat introduced by the smoke closes the channels of the honeycomb body. This configuration has the advantage that there is a safe fire shutdown with simultaneous smoke shutdown, while gas can pass through the honeycomb body before the suspension is released, for example in air conditioning systems.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung wird das erfindungsgemäße Halbzeug in einer Vorrich¬ tung mit rotierendem scheibenförmigen Wabenkörper einge¬ setzt, dessen Sektoren abwechselnd verfahrenstechnisch unterschiedlichen Medienströme ausgesetzt sind. , Derartige Vorrichtungen werden beispielsweise in Gasbe- und/oder -entfeuchtungsanlagen, in Absorptionseinrichtungung, als Katalysatoren oder Wärmetauscher eingesetzt. Durch die Rotation des Wabenkörpers werden hierbei Segmente des Wabenkörpers abwechselnd unterschiedlichen Medienströmen ausgesetzt, beispielsweise Warm- und Kaltluft in Wärmetau¬ schern von Klimaanlagen. Derartige Wabenkörper sind übli¬ cherweise mit Innenantrieb und Innenlagerung ausgestattet, wobei diese nach einer weiteren vorteilhaften Ausgestal¬ tung der Erfindung durch einen Außenantrieb und vorzugswei¬ se auch eine Außenlagerung des Wabenkörpers ersetzt sein können. Hierdurch ergibt sich der Vorteil, daß Antrieb und Lager nicht möglicherweise aggressiven Gasströmen ausge¬ setzt sind, die diese zerstören könnten.According to a further advantageous embodiment of the invention, the semifinished product according to the invention is used in a device with a rotating disk-shaped honeycomb body, the sectors of which are alternately exposed to different media flows in terms of process technology. Such devices are used for example in gas humidification and / or dehumidification systems, in absorption devices, as catalysts or heat exchangers. Due to the rotation of the honeycomb body, segments of the honeycomb body are alternately exposed to different media flows, for example hot and cold air in heat exchangers of air conditioning systems. Such honeycomb bodies are usually equipped with an inner drive and inner bearing, which, according to a further advantageous embodiment of the invention, can be replaced by an outer drive and preferably also an outer bearing of the honeycomb body. This has the advantage that the drive and bearing are not possibly exposed to aggressive gas flows which could destroy them.
Nach einer vorteilhaften Weiterbildung dieser Merkmale ist die Wabenkörperscheibe fest installiert, während die An- und Abströmhauben für die unterschiedlichen Medienströme relativ zu dieser drehbar sind. Nach einer vorteilhaften Ausgestaltung der Erfindung wird das erfindungsgemäße Halbzeug in einer Luftaufbereitungs¬ und -konditionierungsanlage eingesetzt. Hierbei können die verschiedenen Eigenschaften des Wabenkörpers einzeln oder in Kombination vorteilhaft eingesetzt werden, so beispiels¬ weise katalytische Eigenschaften und Filter- bzw. Gastrenn¬ eigenschaften zur Reinigung von lösungsmittelhaltiger Abluft, Adsorptions- und Wärmetauscheigenschaften in Klima¬ anlagen usw.. Ebenso kann das erfindungsgemäße Halbzeug in Gasaufbereitungsanlagen zur Kühlung von Gasen durch Entfeuchtung dienen, wodurch son?t benötigte, unschöne Kühltürme entfallen.According to an advantageous development of these features, the honeycomb body disk is permanently installed, while the inflow and outflow hoods can be rotated relative to the different media flows. According to an advantageous embodiment of the invention, the semi-finished product according to the invention is used in an air conditioning and conditioning system. The various properties of the honeycomb body can be used advantageously individually or in combination, for example catalytic properties and filter or gas separation properties for cleaning solvent-containing exhaust air, adsorption and heat exchange properties in air conditioning systems, etc. Likewise, the invention Semi-finished products in gas processing plants are used to cool gases by dehumidification, which eliminates the need for unsightly cooling towers.
Nach einer weiteren vorteilhaften Austaltung der Erfindung dient das Halbzeug als Geschirr oder Sanitärkeramik. Aus der zur Grundform gestapelten Vorform kann ein solches Geschirr bzw. eine solche Keramik durch Tiefziehen herge¬ stellt werden, wobei im gleichen Arbeitsgang bzw. mit dem selben Werkzeug das Aufweiten der Grundform erfolgen kann. Hierbei sind vorteilhafterweise tiefziehbare Keramikgefäße wie Teller, Becher herstellbar, ebenso wie tiefziehbare Waschbecken, Badewannen. Das Aufweiten der Grundform kann hierbei beispielsweise durch Vakuumeinsatz erfolgen. Nach dem Tiefziehen und Aufweiten wird das Halbzeug, wie oben beschrieben, zu einem Keramikkörper gesintert. Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung, die auch für sich beansprucht wird, wird das Halb¬ zeug als Elektrode in Elektrolyseeintrichtungen oder in einer Brennzelle wie Akkumulator oder Batterie verwendet. Diese Ausgestaltung hat den Vorteil, daß die Elektrode eine äußerst große Reaktionsoberfläche aufweist, die auch eine gute Wärmeabfuhr bewirkt.According to a further advantageous embodiment of the invention, the semi-finished product is used as tableware or sanitary ware. Such dishes or ceramics can be produced from the preform stacked to form the basic shape by deep drawing, it being possible for the basic shape to be expanded in the same operation or with the same tool. Here, deep-drawn ceramic vessels such as plates, cups, as well as deep-drawn wash basins, bathtubs, can advantageously be produced. The basic shape can be expanded, for example, by using a vacuum. After deep drawing and expanding, the semi-finished product is sintered to a ceramic body, as described above. According to a further advantageous embodiment of the invention, which is also claimed for itself, the semi-finished product is used as an electrode in electrolysis devices or in a fireplace insert such as an accumulator or battery. This configuration has the advantage that the electrode has an extremely large reaction surface, which also brings about good heat dissipation.
Nach einer vorteilhaften Weiterbildung dieser Merkmale ist das Halbzeug aus einem Photohalbleiter wie Tiθ2, Gallium oder Germanium gebildet. Diese Ausgestaltung hat den Vor¬ teil, daß Lichtenergie zur Elektrolyse verwendet werden kann, wobei der erfindungsgemäße Wabenkörper lichtdurchläs¬ sig ist, so daß die gesamte große Oberfläche der Wabenkör- perelektrode aktiv ist. Bei einem erfindungsgemäßen Waben¬ körper besteht zudem der Vorteil, daß durch die äußerst dünnen erzielbaren Wandstärken eine gute Lichtdurchlässig¬ keit auch an sich nicht lichtdurchlässiger Materialien gegeben ist.According to an advantageous development of these features, the semifinished product is formed from a photo semiconductor such as TiO 2, gallium or germanium. This embodiment has the advantage that light energy can be used for electrolysis, the honeycomb body according to the invention being translucent, so that the entire large surface of the honeycomb body electrode is active. In the case of a honeycomb body according to the invention, there is also the advantage that the extremely thin achievable wall thicknesses give good translucency even of materials which are not translucent per se.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung besteht das Halbzeug aus anorganischem, vorzugsweise keramischem, durchscheinendem oder transparentem Material und wird als Wärmestrahlungsabsorber verwendet, indem das Halbzeug auf einer oberflächlich oder durchgehend dunkel eingefärbten Grundplatte, bevorzugt ebenfalls aus kerami¬ schem Werkstoff, angeordnet ist. Derartige Wärmestrahlungs¬ absorber, die auf dem Prinzip des Eisbärfelles beruhen, sind an sich bekannt. Diese sind jedoch nicht hitzebestän¬ dig oder nicht wetterfest, da sie entweder aus Kunststoff oder aus Glas bestehen. Durch den erfindungsgemäßen Waben¬ körper aus keramischem Material ist ein solcher Wärmestrah¬ lungsabsorber jedoch hitzebeständig, wetterfest und ver¬ gleichsweise leicht. Durch die dunkle, insbesondere schwar¬ ze Grundfläche ist eine hohe Wärmeabsorption gegeben, während die Kanäle des Wabenkörpers die Wiederabstrahlung der aufgenommenen Wärme vermindern. Durch die Transparenz des Keramikmaterials ist Strahlabsorption bei beliebigem Einstrahlungswinkel möglich. Die dunkle Grundplatte er¬ setzt hierbei die Haut des Eisbären, während der Wabenkör¬ per die Haare des Eisbärfelles ersetzt.According to a further advantageous embodiment of the invention, the semifinished product consists of inorganic, preferably ceramic, translucent or transparent material and is used as a heat radiation absorber in that the semifinished product is arranged on a surface plate which is darkened on the surface or throughout, preferably also made of ceramic material . Such heat radiation absorbers, which are based on the principle of polar bear fur, are known per se. However, these are not heat-resistant or not weatherproof, since they are either made of plastic or made of glass. Due to the honeycomb body made of ceramic material according to the invention, however, such a heat radiation absorber is heat-resistant, weatherproof and comparatively light. The dark, in particular black, base area provides high heat absorption, while the channels of the honeycomb body reduce the re-radiation of the absorbed heat. The transparency of the ceramic material enables beam absorption at any angle of incidence. The dark base plate replaces the skin of the polar bear, while the honeycomb body replaces the hair of the polar bear fur.
Ein solcher Wärmestrahlungsabsorber kann vorteilhafterwei¬ se als Focus-Receiver in Sonnenenergieanlagen verwendet werden, da er hitzebeständig ist und daher nicht gekühlt werden muß. Er kann daher auch zur direkten ölraffinierung im Focus-Receiver einer Sonnenenergieanlage eingesetzt werden. Besonders vorteilhaft ist die Verwendung nichtoxi- discher Keramik, da diese besonders große Hitzebständig- keit aufweist.Such a heat radiation absorber can advantageously be used as a focus receiver in solar energy systems, since it is heat-resistant and therefore does not have to be cooled. It can therefore also be used for direct oil refining in the focus receiver of a solar energy system. The use of non-oxide ceramics is particularly advantageous since it has a particularly high heat resistance.
Eine solcher Wärmestrahlungsabsorber kann vorteilhafterwei¬ se auch in Kombination mit einer Wärmekraftmaschine betrie¬ ben werden. Eine solche Wärmekraftmaschine kann beispiels¬ weise ein Stirlingmotor sein, der direkt oder indirekt erwärmt wird, oder eine Dampfturbine oder sonstige dampfbe¬ triebene Maschine, wobei im Focus-Receiver der Dampf er¬ zeugt wird oder eine Wärmeübertragungsmittel erwärmt wird, welches andernorts Dampf erzeugt. Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung wird ein solcher Wärmestrahlungsabsorber als Fassaden¬ verkleidung von Gebäuden verwendet. Hierbei dient der Wärmestrahlungsabsorber bevorzugt gleichzeitig als Wärmeisolierung und zur Wärmeenergiegewinnung.Such a heat radiation absorber can advantageously also be operated in combination with a heat engine. Such a heat engine can be, for example, a Stirling engine that is heated directly or indirectly, or a steam turbine or other steam-operated machine, the steam being generated in the focus receiver or a heat transfer medium being heated, which generates steam elsewhere. According to a further advantageous embodiment of the invention, such a heat radiation absorber is used as the facade cladding of buildings. Here, the heat radiation absorber is preferably used at the same time as thermal insulation and for heat energy generation.
Nach einer anderen vorteilhaften Ausgestaltung der Erfin¬ dung ist ein solcher Wärmestrahlungsabsorber quer zur Fassade eines Gebäudes eingebaut. Hierbei dient dieser ausschließlich zur Wärmeenergiegewinnung und zwar beispielsweise, indem die Grundplatte und/oder der Waben¬ körper ins Innere des Gebäudes verlängert sind, wo diese als Heizelement, beispielsweise Kochplatte, dienen. Selbst¬ verständlich kann diese Ausgestaltung auch zur sonstigen Wärmeenergiegewinnung verwendet werden.According to another advantageous embodiment of the invention, such a heat radiation absorber is installed transversely to the facade of a building. In this case, this is used exclusively for heat energy generation, for example by extending the base plate and / or the honeycomb body into the interior of the building, where they serve as a heating element, for example a hotplate. Of course, this embodiment can also be used for other heat energy generation.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient ein solcher Wärmestrahlungsabsorber zur Wärmeisolierung, indem das Halbzeug zwischen zwei oberflächlich oder durchgehend dunkel eingefärbten Platten angeordnet ist. Der Wabenkörper tritt hierbei an die Stel¬ le von sonst üblicher Mineralwolle, die physiologisch bedenklich ist. Durch die Wabenstruktur ergibt sich neben der Isolatorwirkung auch eine hohe mechanische Festigkeit, insbesondere wenn die Kanäle des Halbzeugs senkrecht zu den dunkel eingefärbten Platten verlaufen. Hierbei gründet sich die Wärmeisolation auf die hohe Reflexion in den Kanälen des Halbzeugs, die noch dadurch erhöht werden kann, daß diese, ebenso wie die Innenseiten der Grundplat¬ ten, mit einer Wärmestrahlungsreflektierenden Schicht ver- sehen sind. Hierdurch wird eine solche Wärmeisolierung auch besonders geeignet für den Einsatz als Hitzeschild bei Raumfahrzeugen, wo eine besonders hohe mechanische Sta¬ bilität gefordert ist.According to a further advantageous embodiment of the invention, such a heat radiation absorber is used for heat insulation, in that the semifinished product is arranged between two sheets which are colored dark on the surface or throughout. The honeycomb body takes the place of the otherwise usual mineral wool, which is physiologically questionable. The honeycomb structure provides not only the insulator effect but also a high mechanical strength, especially if the channels of the semi-finished product run perpendicular to the dark colored plates. In this case, the thermal insulation is based on the high reflection in the channels of the semi-finished product, which can be increased further by the fact that, like the inside of the base plates, this is combined with a layer reflecting heat radiation. are seen. In this way, such thermal insulation is also particularly suitable for use as a heat shield in spacecraft, where particularly high mechanical stability is required.
Nach einer weiteren vorteilhaften Ausgestaltung der Erfin¬ dung dient das erfindungsgemäße Halbzeug als Feststoffhy¬ dridspeicher in einem Kreisprozeß mit Metallhydriden un¬ terschiedlicher Bildungs- und Zersetzungstemperatur, auch in Verbindung mit einer Wärmekraftmaschine. In einem sol¬ chen Kreisprozeß wird Wasserstoff aus einem Metallhydrid¬ speicher durch Erwärmung ausgetrieben und einem zweiten Feststoffhydridspeicher zugeführt, welcher den Wasserstoff bindet. Der Feststoffhydridspeicher hoher Bildungs- und Zersetzungstemperatur, beispielsweise Magnesiumwabenkör¬ per, wird, bevorzugt in Verbindung mit einem erfindungsge¬ mäßen Wärmestrahlungsabsorber, insbesondere durch Sonne¬ nenergie erwärmt und der Wasserstoff ausgetrieben. Dieser Wasserstoff wird einem zweiten Feststoffhydridspeicher mit niedriger Bildungs- und Zersetzungstemperatur, beispiels¬ weise Titaneisenwabenkorper, zugeführt, wo er wiederum gebunden wird. Der hierin gespeicherte Wasserstoff kann bereits bei niederer Temperatur, beispielsweise durch Abwasserwärme, ausgetrieben werden und in den Feststoffhy¬ dridspeicher hoher Bildungstemperatur zurückgeführt wer¬ den. Die bei der Adsorption freigesetzte Wärmeenergie kann entweder Wärmekraftmaschinen zugeführt werden oder direkt als Heizwärme verwendet werden. Der Vorteil des erfindungs- gemäßen Halbzeugs besteht darin, daß eine große Reakti¬ onsoberfläche zur Verfügung gestellt wird und der Speicher besser be- und entladbar ist als herkömmliche Speicher. According to a further advantageous embodiment of the invention, the semifinished product according to the invention serves as a solid hydride storage in a cycle with metal hydrides of different formation and decomposition temperatures, also in connection with a heat engine. In such a cycle hydrogen is expelled from a metal hydride storage by heating and fed to a second solid hydride storage which binds the hydrogen. The solid hydride storage at a high formation and decomposition temperature, for example magnesium honeycomb body, is preferably heated in connection with an inventive heat radiation absorber, in particular by solar energy, and the hydrogen is driven off. This hydrogen is fed to a second solid hydride storage with a low formation and decomposition temperature, for example titanium iron honeycomb bodies, where it is in turn bound. The hydrogen stored therein can already be driven off at a low temperature, for example by waste water heat, and can be returned to the solid hydride storage at a high formation temperature. The heat energy released during adsorption can either be supplied to heat engines or used directly as heating energy. The advantage of the invention According to the semi-finished product, a large reaction surface is made available and the storage is easier to load and unload than conventional storage.
Claims
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3932211 | 1989-09-27 | ||
| DEP3932211.4 | 1989-09-27 | ||
| DE4010072 | 1990-03-29 | ||
| DEP4010072.3 | 1990-03-29 | ||
| DEP4019346.2 | 1990-06-18 | ||
| DE4019346 | 1990-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1991004779A1 true WO1991004779A1 (en) | 1991-04-18 |
Family
ID=27200261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE1990/000736 Ceased WO1991004779A1 (en) | 1989-09-27 | 1990-09-27 | Process for the production of a semi-finished article, and uses of the article thus produced |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU6418990A (en) |
| DE (1) | DE4030626A1 (en) |
| WO (1) | WO1991004779A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014006379A1 (en) * | 2014-05-05 | 2015-11-05 | Gkn Sinter Metals Engineering Gmbh | Hydrogen-storing components of slip and apparatus and method therefor |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB628180A (en) * | 1946-07-24 | 1949-08-24 | George May | Improvements in or relating to structural elements made from paper and like sheets |
| US3210233A (en) * | 1962-08-27 | 1965-10-05 | Mcdonnell Aircraft Corp | Heat insulating and ablative structure and method of making same |
| US3321355A (en) * | 1964-04-20 | 1967-05-23 | Hexcel Products Inc | Fabric reinforced plastic product and method of making same |
| US3661644A (en) * | 1966-12-19 | 1972-05-09 | Mc Donnell Douglas Corp | Battery construction having a honeycomb matrix with cells filled with different electrode materials |
| US3840425A (en) * | 1972-03-31 | 1974-10-08 | Avco Corp | Reticulated fire protecting structure |
| US4767656A (en) * | 1984-01-09 | 1988-08-30 | The Boeing Company | Composite material structure with integral fire protection |
| DE3809350A1 (en) * | 1988-03-19 | 1989-09-28 | Hoechst Ceram Tec Ag | METHOD FOR INCREASING THE COMBUSTION CONSTRUCTION OF CERAMIC FILM POWERS |
| DE3809694A1 (en) * | 1988-03-23 | 1989-10-05 | Hoechst Ceram Tec Ag | METHOD FOR PRODUCING A RELEASE AGENT FOR MULTI-LAYER BURNING CERAMIC FILMS |
| DE3840137C1 (en) * | 1988-11-29 | 1990-03-29 | Feldmuehle Ag, 4000 Duesseldorf, De | |
| US4921616A (en) * | 1986-03-19 | 1990-05-01 | Ceramiques Et Composites | Alveolar ceramic filters for high melting metals |
| US4921744A (en) * | 1988-01-27 | 1990-05-01 | Ube Industries, Ltd. | Honeycomb structure of aromatic polyimide |
| US4921745A (en) * | 1987-12-25 | 1990-05-01 | Ube Industries, Ltd. | Honeycomb structure of aromatic polyimide |
-
1990
- 1990-09-27 WO PCT/DE1990/000736 patent/WO1991004779A1/en not_active Ceased
- 1990-09-27 AU AU64189/90A patent/AU6418990A/en not_active Abandoned
- 1990-09-27 DE DE4030626A patent/DE4030626A1/en not_active Withdrawn
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB628180A (en) * | 1946-07-24 | 1949-08-24 | George May | Improvements in or relating to structural elements made from paper and like sheets |
| US3210233A (en) * | 1962-08-27 | 1965-10-05 | Mcdonnell Aircraft Corp | Heat insulating and ablative structure and method of making same |
| US3321355A (en) * | 1964-04-20 | 1967-05-23 | Hexcel Products Inc | Fabric reinforced plastic product and method of making same |
| US3661644A (en) * | 1966-12-19 | 1972-05-09 | Mc Donnell Douglas Corp | Battery construction having a honeycomb matrix with cells filled with different electrode materials |
| US3840425A (en) * | 1972-03-31 | 1974-10-08 | Avco Corp | Reticulated fire protecting structure |
| US4767656A (en) * | 1984-01-09 | 1988-08-30 | The Boeing Company | Composite material structure with integral fire protection |
| US4921616A (en) * | 1986-03-19 | 1990-05-01 | Ceramiques Et Composites | Alveolar ceramic filters for high melting metals |
| US4921745A (en) * | 1987-12-25 | 1990-05-01 | Ube Industries, Ltd. | Honeycomb structure of aromatic polyimide |
| US4921744A (en) * | 1988-01-27 | 1990-05-01 | Ube Industries, Ltd. | Honeycomb structure of aromatic polyimide |
| DE3809350A1 (en) * | 1988-03-19 | 1989-09-28 | Hoechst Ceram Tec Ag | METHOD FOR INCREASING THE COMBUSTION CONSTRUCTION OF CERAMIC FILM POWERS |
| DE3809694A1 (en) * | 1988-03-23 | 1989-10-05 | Hoechst Ceram Tec Ag | METHOD FOR PRODUCING A RELEASE AGENT FOR MULTI-LAYER BURNING CERAMIC FILMS |
| DE3840137C1 (en) * | 1988-11-29 | 1990-03-29 | Feldmuehle Ag, 4000 Duesseldorf, De |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4030626A1 (en) | 1991-05-29 |
| AU6418990A (en) | 1991-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3877633B1 (en) | Catalytically active particle filter with a high degree of filtration efficiency | |
| DE60027688T2 (en) | Honeycomb structure with corrugated walling and method of making same | |
| DE10323607B4 (en) | Device for cleaning exhaust gases of an internal combustion engine | |
| DE102010009449B4 (en) | honeycomb filter | |
| CN103270002B (en) | Method for applying a discriminating layer on a porous ceramic filter via a gas-borne porous assembly | |
| DE3823732C2 (en) | Catalyst for cracking ozone | |
| KR20160093060A (en) | Wall-flow filter comprising catalytic washcoat | |
| DE1646889A1 (en) | Ceramic honeycomb product | |
| JP2017523040A (en) | Method for producing a catalyst and catalyst article | |
| EP2095865A1 (en) | Device for reducing dibenzo-dioxin and dibenzo-furan and particle emissions | |
| DE102014119178A1 (en) | Selective catalytic reduction processes using doped ceria | |
| DE102014013893A1 (en) | Catalyst loaded honeycomb filter | |
| EP4010114A1 (en) | Catalyser substrates with porous coating | |
| DE60218100T2 (en) | Catalyst for vehicles | |
| DE2631092A1 (en) | CERAMIC ALTERNATING LAYER HEAT EXCHANGER IN MODULAR DESIGN | |
| EP4015064B1 (en) | Catalytically active particle filter with high filtration efficiency | |
| DE4028720A1 (en) | Ceramic honeycomb body useful as catalyst in IC. engines - comprises materials of high electric constant and is fitted with microwave radiator | |
| WO1991004779A1 (en) | Process for the production of a semi-finished article, and uses of the article thus produced | |
| CH713958A1 (en) | System comprising a carrier with flow channels and at least one catalytically active substance. | |
| KR102756772B1 (en) | Ozone decomposing catalyst and method for fabricating the same | |
| EP2145663B1 (en) | Catalyst for converting nitrous oxide and its application in industrial nitric acid production | |
| WO1991013714A1 (en) | Process for manufacturing metallic or ceramic materials | |
| DE2202152A1 (en) | Catalyst carrier | |
| WO2013072264A1 (en) | Heat-insulating insulation element for high-temperature applications and a procedure for manufacturing it | |
| KR20120110758A (en) | Photo catalyst filter and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BG BR CA FI HU JP KR NO RO SU US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE |
|
| NENP | Non-entry into the national phase |
Ref country code: CA |
|
| WR | Later publication of a revised version of an international search report |