WO2005061079A1 - Abgasnachbehandlungsanordnung - Google Patents
Abgasnachbehandlungsanordnung Download PDFInfo
- Publication number
- WO2005061079A1 WO2005061079A1 PCT/DE2004/002555 DE2004002555W WO2005061079A1 WO 2005061079 A1 WO2005061079 A1 WO 2005061079A1 DE 2004002555 W DE2004002555 W DE 2004002555W WO 2005061079 A1 WO2005061079 A1 WO 2005061079A1
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- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- support structure
- fibers
- arrangement according
- aftertreatment arrangement
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
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- 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
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- 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
- B01D39/2027—Metallic material
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- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0226—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being fibrous
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- 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
- F01N3/2835—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support fibrous
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- 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
- F01N2330/12—Metallic wire mesh fabric or knitting
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- 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
- F01N2330/14—Sintered material
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- 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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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- 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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention is based on an exhaust gas aftertreatment arrangement or a method for producing the exhaust gas aftertreatment arrangement according to the type of the independent claims. It is known to denit exhaust gas from motor vehicles using NOx storage catalytic converters or to remove soot using a particle filter. Catalyst layers are sometimes used to improve the oxidation of CO and hydrocarbons in diesel oxidation catalysts and to improve soot regeneration in diesel particulate filters. It is known, for example from WO 01/36097 AI, to often apply catalyst layers (layers which contain active material, namely catalyst material) to a basic structure together with a coating which increases the surface area because it is uneven, a so-called washcoat. Technically, this can be achieved in the following way.
- the exhaust gas aftertreatment arrangement or support structure according to the invention or the method according to the invention for producing the exhaust gas aftertreatment arrangement with the characterizing features of the independent claims have the advantage that the fiber-rich surface layer enables a highly porous surface structure with a large surface area, whereby the invention enables the pressure drop behavior, in particular of To improve soot-laden sintered metal filters by reducing the increase in exhaust gas back pressure when soot is loaded, to create a good gas-solid contact, to allow better contact for the oxidation of the exhaust gas and the soot and to provide a larger area for catalytic coatings, in particular in the case of diesel oxidation filters integrated on sintered metal filters. To provide catalysts or in NO x storage catalysts.
- the measures listed in the dependent claims permit advantageous developments and improvements of the exhaust gas aftertreatment arrangement or support structure or of the specified method for producing the exhaust gas aftertreatment arrangement specified in the independent claims.
- the use of sintered metal in the construction of the aftertreatment arrangement ensures a robust and long-lasting arrangement even under extreme thermal conditions, in particular a flexible choice of the construction of such an arrangement in comparison to ceramic arrangements, in which one is free in the choice of the design due to the usual Manufacturing method used, namely continuous casting of the ceramic body is limited.
- the exhaust gas aftertreatment arrangement is designed as a particle filter using sintered metal, it has a longer service life than comparable ceramic filters. Due to the freedom of design, the filter construction can be selected so that if the filter for soot accumulation always needs to be regenerated, the soot starts to burn in several places at the same time and not only on one side of the filter, as is normally the case with ceramic filters. This results in a more balanced and therefore life-increasing thermal stress. In particular, there is the advantage of an increased service life also because the ash storage volume is increased by the layer of fibers. Ash is the sum of the residues that remain in the filter even after regeneration of the particle filter, accumulate over many regeneration cycles and ultimately lead to the filter “ash death”.
- This ash death can advantageously be delayed by means of the fiber layer.
- the exhaust gas back pressure of a sintered metal filter is advantageously reduced due to a synergy effect when combining a fiber layer with depth filter effect and the surface filter made of sintered metal.
- the fiber layer acting as a depth filter does not form a filter cake that closes the continuous pores of the fiber layer, which means that only a low exhaust gas counterpressure even when the particle filter or the flow-filtering arrangement is ensured, which is advantageously combined with the boundary layer, which acts as a surface filter, between the fiber layer and the sintered metal volume, which has a high filter ration efficiency.
- the filter pockets can thereby be arranged closer together without falling below a certain minimum distance between the walls of adjacent filter pockets, in particular at the downstream end of a filter according to DE 102 23 452 AI, which allows the exhaust gas back pressure to rise slightly can.
- the exhaust gas aftertreatment arrangement is produced with sintered metal walls that have a varying thickness, in particular from a metal grille with openings that are only partially filled with sintered metal, then in addition to saving material on sintered metal, there is also a more compact arrangement that can be positioned even closer to an adjacent sintered metal wall and still leaves enough space to keep the exhaust gas counter pressure at an acceptable level during the entire life of the exhaust gas aftertreatment arrangement when a so-called filter cake grows on ash in the case of a soot or particle filter. In addition, the exhaust gas back pressure is further reduced without having to accept any loss in filtration efficiency.
- the large-volume layer with high porosity in the case of a particle filter leads to a particularly loose, more reactive deposit of the soot.
- Such an embodiment is therefore particularly suitable for the collection and loose storage of soot.
- a large active surface is advantageously obtained and optionally, when applying or introducing catalytic material, a high catalytic activity and thus effective cleaning of the exhaust gas due to the large and three-dimensional surface and good soot or gas-catalyst contact; this leads to a relatively low N0 2 soot combustion temperature (balance point temperature), low regeneration temperature, shorter Regeneration time, increase in the volume of washcoat that can be applied (eg with integrated diesel oxidation catalyst (DOC) on sintered metal filters (SMF), and or NO x storage catalyst coating.
- DOC diesel oxidation catalyst
- SMF sintered metal filters
- the washcoat advantageously strengthens the adhesion between catalytically active material and the fiber structure and, in the case of fibers coated with washcoat, further increases the active fiber surface. Another advantage is that when using a washcoat to connect the fibers, a special binder is not necessary and the production is simple and inexpensive.
- the fiber structure can advantageously be produced in advance independently of the support structure / filter as a highly porous fiber mat and only then applied to the filter surface. This leads to simple technical implementation and manageability, especially when the fiber layer is coated or dislodged with catalytically active material, because the fiber mat only makes up a fraction of the total weight of a filter and is therefore easy to transport compared to an entire filter structure. Furthermore, there is a wide range of applications.
- the fiber mat and thus the fiber layer on the sintered metal can be set precisely in advance and checked with regard to geometry, in particular layer thickness, but also with regard to chemical or mesoscopic composition.
- an exhaust gas aftertreatment arrangement with fiber mat has a higher structural stability than an arrangement with fiber layers produced by sedimentation.
- the fiber mats can be provided with catalytically active coatings independently of the sintered metal filter will: the coatings can be made on the ceramic material of the fibers, the coating of which is easier to implement than that of metallic supports; The ceramic fibers are chemically more resistant than the SMF base material, especially at high temperatures.
- the catalytic coating is locally separated from the sintered metal filter and the coating solution ("slurry") and the washcoat have only minimal contact with the steel surface, whereby chemical attacks such as corrosion can be avoided.
- a high washcoat loading of the fibers is possible, especially for Nox storage catalytic converter coatings without blocking the sintered metal structure with washcoat or slurry, which means that the back pressure of the filter can be kept low
- Coating compositions are used by using differently prepared fiber mats on different bags.
- Fibers with a diameter of 1 to 3 micrometers, in particular 2 to 3 micrometers ensure a high active fiber surface while at the same time being harmless to health by avoiding the risk of cancer, which would exist if even finer fibers were used.
- a wavy fiber layer advantageously leads to a further increase in the surface area, a higher soot storage capacity and, as a result, a reduced back pressure rise due to soot loading.
- the fiber layer or support structure applied to a support structure is also included as such by the invention.
- washcoat designates partly the ready-to-use layer, partly the material from which the actual layer is made.
- FIG. 1 shows schematically, in a representation combining a longitudinal section and a perspective view, a section of a catalytic converter or catalytically coated exhaust gas filter with a three-dimensional support structure which is supported on and supported by a support structure.
- 2 a-c shows the structure of various support structures
- FIG. 3 shows an alternative structure of a support structure
- FIG. 4 a-c fiber-coated support structures
- FIG. 5 a-b fiber-coated support structures with a corrugated surface
- FIG. 6 a-c support structures with non-woven fabric.
- FIG. 1 shows a special formulation of a washcoat for soot filter systems based on sintered metal, which are coated mainly with catalytic - but also non-catalytic - (but also for other soot filter systems).
- a major improvement is the use of a high proportion (ratio) of fibers, especially long fibers, in the washcoat. When applied or stacked on filter materials or a support structure, these fibers allow highly porous, three-dimensional support structures for catalyst material with a thickness of 0.05 mm to 2.0 mm and a porosity of more than 50% to be formed.
- FIG. 1 shows a support structure F which is part of a catalytic converter for diesel engines.
- the support structure F has metallic wall sections 2, between which a rigid layer 3 formed in the example from metal balls is arranged, on which a three-dimensional support structure S is supported and connected to the support structure as firmly as is required for reliable operation of the catalytic converter.
- the support structure S has fibers 5, which in the example consist of ceramic. In the example, the fibers 5 are straight sections of limited length. Each individual fiber 5 is shown in longitudinal section.
- the individual fibers 5 are arranged in a three-dimensional, random state.
- the fibers 5 are almost all coated with a coating, a so-called washcoat 6, which has an irregular outer contour and surrounds the fibers over their entire circumference, inter alia, in order to enlarge the surface.
- the washcoat can also cover the ends of the fibers 5.
- Some fibers 5 are shown in the figure without a washcoat; this can happen accidentally, but it can also be intentional during production.
- the washcoat 6 carries active material 8 on its outside, namely catalyst material. This is symbolized in the figure by individual very small balls.
- the active material 8 does not necessarily have to envelop all of the fibers over a large area or completely, but that it may be sufficient if the active material is applied to the washcoat as a more or less strongly interrupted layer.
- the individual fibers 5 lie in a direction perpendicular to the plane of the drawing seen at the bottom part, partly at the top, partly extend from the bottom to the top, so they fill the space formed by them 'in three dimensions and form a spatial structure which is similar to that of a nonwoven (in English "non-woven fabric").
- a support structure S for an internal combustion engine exhaust gas filter the effective area of which compared to a base area of the support structure by three-dimensional design of the effective Area is enlarged, the support structure optionally active (namely catalytic active) material, the support structure S having three-dimensionally arranged fibers 5, which leave open-pored cavities between them, and wherein fibers 5 are connected to one another in the region of mutually adjacent regions by a binder.
- the cohesion of the fibers 5 is brought about by the washcoat 6, which is solid after production, or by inorganic binder materials (binders, see above) in the region of the contact points of the fibers 5. It is not absolutely necessary for all points of contact or adjacent regions of the fibers to be firmly connected to one another.
- the layer 3 of the support layer F is formed from very small metal spheres, which are connected by sintering and leave open-pored, gas-permeable interstices free, so that a sintered metal filter (SMF) results overall.
- SMF sintered metal filter
- the supporting layer or supporting structure with the active material on it intercepts soot from the diesel exhaust gases in the example, and converts this soot into CO 2 with the participation of active material 8 in the presence of oxygen (and / or NO 2 ).
- the active material 8 also causes a conversion of nitrogen oxides (NO ⁇ ) into nitrogen and oxygen.
- the layer 3 is impermeable to gas, and the flow of the exhaust gas runs horizontally in the illustration in FIG. 1.
- the support structure is designed as a flow-through substrate, that is to say the support structure is not open-porous, that is to say does not have any pores which are permeable to gas, but is at most porous on the surface to enlarge the gas contact area.
- a flow-through arrangement such as, for example, an oxidation catalytic converter, in particular a diesel Oxidation catalyst, in addition to metal or ' Sintered metal can also be made from silicon carbide or cordierite.
- the fibers 5 have a diameter in the range from 1 to 10 micrometers, in the above exemplary embodiment a thickness of approximately 5 micrometers. It is advantageous to use fibers from a thickness of 3 micrometers upwards, since these have sufficient thermo-mechanical strength and provide a sufficiently large active surface. In alternative embodiments, fibers with a diameter of 1 to 3 micrometers can also be provided, in particular between 2 and 3 micrometers, as a result of which a structure with a particularly high porosity can be produced.
- the fibers used have the property of being able to serve as a carrier for a catalytic coating, in particular for exhaust gas aftertreatment of internal combustion engines.
- fibers of greater length can also be provided in embodiments of the invention, which then form a three-dimensional structure of a support structure in a wound, woven, crimped or braided arrangement, thus in one irregular or even regular arrangement, may be provided (supporting structure with randomly arranged fibers).
- a woven arrangement can preferably be made in a linen weave; it has a first layer of parallel fibers, over which a second parallel layer of fibers with a longitudinal direction offset by 90 ° is arranged, the fibers of which are interwoven with those of the first layer as in a linen fabric ( Support structure with fibers arranged according to an order principle).
- the fibers contained in the support structure S have an active fiber surface of at least 1 square meter per gram of fiber weight.
- an active fiber surface can be advantageously achieved which exceeds the value of 30 square meters per gram of fiber weight.
- the active material 8 Any material suitable for soot catalysts and / or NOx storage catalysts can be considered as the active material.
- the active material 8 also supports the conversion of CO into C0 2 and of hydrocarbons in the exhaust gas into water and C0 2 .
- the material of the fibers, ceramic is A1 2 0 3 in the exemplary embodiment. Instead, or in a mixture, Ti0 2 and Si0 2 can be provided for the ceramic in embodiments of the invention.
- the washcoat may be formed from the same oxides just mentioned, either one of the oxides, or a mixture. In the example, A1 2 0 3 is also provided here.
- the support structure F used in the case of the configuration of the exhaust gas aftertreatment arrangement as a wall flow filter, in particular as a sintered metal particle filter having filter pockets similar to that described in DE 10301037, preferably has an average pore diameter which is greater than 6 micrometers is the proportion of pores with one Pore diameters above 10 microns in the total number of pores in the support structure are greater than 10 percent, and the porosity of the support structure is above 30 percent.
- the above information relates to the average pore diameter, proportion of pores with pores larger than 10 micrometers and porosity on the areas of the filter bag walls that are formed by the open-pored sintered metal.
- the support structure can also be designed as a wall flow filter, for example as a silicon carbide filter or as a filter which is made of cordierite, with corresponding pore dimensions and pore proportions in the total volume, with the advantage of a low exhaust gas back pressure paired with high filtration efficiency.
- This high-volume layer can be produced, for example, in a process with a single step or in two steps:
- a coating mixture with a high proportion of material fibers, a small proportion of material grains (as Binder, among other functions), washcoat additives (in particular Ti0 2 , Si0 2 and / or Al 2 0 3 ) and optionally active compounds (catalytically active material) are used.
- Washcoat material can make the use of the material grains, which for example mainly consist of aluminum oxide, unnecessary.
- the fiber structure can be layered as a first layer to form the three-dimensional support structure on which the material grains plus additives plus active compounds are layered in a second step.
- a simple production method for the three-dimensional base layer of the figure results from the fact that a slurry of fibers 5 is provided in a suspension of particles of the abovementioned oxides or of the binder used in water (or another suitable liquid), so that the fibers and the Binder can be applied in a flowable state.
- the support structure is immersed in the suspension and then pulled out again.
- Another possibility is the application by sucking a slurry through the filter material.
- the solids content of the slurry is adjusted such that a washcoat of suitable thickness is formed on the fibers 5 and that a support layer of the desired thickness, which is advantageously in the range from 0.05 mm to 2.0 mm thickness, is formed on the support structure. formed. After drying (with or without the action of heat), this layer has cavities that are connected to one another between the individual fibers and allow diesel engine exhaust gas to flow through the base layer.
- the dried washcoat material also causes the base layer to adhere firmly to the support structure.
- the fibers are first applied to the support structure F in order to produce the support structure S and, in a further step, provided with binders and connected to one another.
- FIG. 2 shows in partial image a a known expanded metal grille in a top view, as can be used for the production of an expanded metal sintered metal filter. It is a flat, flat metal grid 20 with struts that enclose openings 21.
- Such an expanded metal is a flat material or semi-finished product with openings in the surface, which is created by staggered cuts without loss of material and at the same time stretching deformation.
- the meshes of the material produced in this way are usually diamond-shaped, as also shown in drawing a, but can also be round or square and are neither braided nor welded. The material can be cut to any size without losing its solid internal cohesion or dissolving.
- Such an expanded metal with openings with a cross-sectional area of approximately 0.5 to approximately 5 square millimeters and struts with a width of approximately 0.1 to approximately 1 millimeter can be used to to produce a support structure F according to partial image b or an alternative support structure 26 according to partial image c.
- Sub-picture b shows a periodically continuing section of a support structure F already known from FIG. 1 in a longitudinal sectional side view, in which the metallic wall sections 2 are formed by the expanded metal grid and the rigid layer 3 of metal powder sintered with the expanded metal, which is inserted into the openings 21 of the Expanded metal mesh has been previously introduced;
- This sintered metal powder is shown in the form of metal balls in FIG. 2b and in FIG.
- the rigid layer 3 made of sintered metal has an open-pored structure and a thickness 24 of 0.1 to 0.8 millimeters, in particular approximately 0.5 millimeters, corresponding to the thickness of the expanded metal grid.
- a metal mesh can also be used instead of the expanded metal grid.
- the rigid layer 3 can also be thicker than the expanded metal grid and / or that
- the alternative support structure 26 according to FIG. 2c which likewise shows a section of such a support structure in a longitudinal sectional side view, is produced in a similar manner to the structure according to FIG. 2b, but with the difference that the openings 21 of the expanded metal grid 2 are not completely filled with sintered metal, so that the openings 21 of the expanded metal lattice are closed (except for the open-porous structure of the sintered metal regions 3), but depressions with a height 25 free of sintered metal can still be found in the region of these former openings. At a thickness 24 of the expanded metal grid of 0.5 millimeters, this free height 25 lies in a range between 0.2 and 0.4 millimeters.
- the only partial filling can be achieved in that the expanded metal mesh is passed over a soft, elastic roller or a soft stamp when it is infested with sintered metal powder, so that the depth of the expanded metal is filled to a certain extent. During the filling, the sintered metal can thus penetrate into the expanded mesh spaces to an adjustable degree.
- FIG. 3 shows a periodically continuing section of a further alternative support structure 35, in which the openings of the expanded metal grid 20 have not been filled with metal powder which has subsequently been sintered, but in which a sintered metal foil 30 has been applied, in particular pressed, to one side of the expanded metal grid , has been.
- this sintered metal foil is still a “green”, that is to say not yet sintered metal foil, consisting of a mixture of a sintered metal powder with a binder.
- This metal foil can be produced by extrusion or casting and has a thickness which is smaller than that After the film has been applied to the expanded metal grid under mechanical pressure and heat, in particular by lamination or rolling, sintering takes place, in which the sintered metal also forms an inseparable connection with the expanded metal grid.
- the sintered metal foil 30 likewise has an open-pored structure , and the support structure 35 has depressions between the struts of the expanded metal grid similar to the embodiment of a support structure shown in FIG. 2c.
- FIG. 4a shows the upstream arrangement of a fiber layer S on a support structure F, which is already known from FIG. 1.
- the support structure F in the form of an expanded metal completely filled with sintered metal according to FIG. 2b has a thickness 24 as described above
- the layer of fibers S has a thickness of 42 mm Range from 0.05 to 2 millimeters (see description for FIG. 1).
- the thickness of the entire structure, for example the wall of a filter bag forms as a sintered metal filter according to DE 102 23 452 AI exhaust aftertreatment arrangement is given by the sum of the individual thicknesses 24 and 42.
- the porosity of the fiber layer can be dimensioned so that it functions as a depth filter. This means that the "meshes" of the three-dimensional network formed by the interlinked fibers are very wide. This is particularly the case with a porosity above 60 percent by volume. Even if a particle "docks" on a fiber, it remains due to the large size There is still enough space next to it that further (soot) particles can pass through the pore in question in the fiber layer. A sufficient thickness of the fiber layer ensures, however, that particles are caught with a sufficient probability when flying through the fiber layer on a path towards the rigid region 3.
- the rigid sintered metal region 3 on the other hand, is also open-pored, but because of the smaller-diameter pores, it acts as a surface filter because a pore becomes blocked as soon as a particle becomes lodged in this individual pore.
- FIG. 4b shows an arrangement using an alternative support structure 26 according to FIG. 2c with only half-full openings of the underlying expanded metal grid.
- the original free height 25 is filled with the layer of fibers S.
- the fiber structure is housed within the expanded metal grid and does not protrude on the side facing away from the rigid regions 3 or only slightly beyond the expanded metal grid.
- the thickness of the entire structure is essentially given solely by the thickness 24 of the expanded metal grid used.
- FIG. 4c shows an arrangement using the further alternative support structure 35 according to FIG. 3 with only half-full openings of the underlying expanded metal grid, the openings being filled using a sintered metal foil. The same applies to the thickness of the entire arrangement as explained for FIG. 4b.
- the expanded metal interstices are filled with rigid areas in the form of sintered metal, not on the entire height of the mesh, but only on one side to a certain extent, for example up to half the expanded metal height 24.
- the free space Space in the grid is then filled with a fiber structure from the opposite side.
- the combination of fiber structure and sintered metal lies within the expanded metal structure.
- the height of the filling layer (sum of sintered metal and fiber structure) is the same or slightly larger than the height of the expanded metal. A slight elevation through the fiber structure can be desired in order to cover the entire surface, ie not only the gaps, but also the webs of the expanded metal grid, with filtering fibers.
- the filtration efficiency of the combination of depth-filtering fiber layer and the surface filter made of sintered metal is over 90 percent, depending on the dimensioning or application also over 99 percent.
- the percentage specifies the filtered volume flow.
- the total thickness of the arrangement is reduced, with the consequence of a comparatively lower exhaust gas back pressure in the case of a flow-filtering arrangement.
- the filter pockets can thereby be arranged closer together without falling below a certain minimum distance between the walls of adjacent filter pockets, in particular at the downstream end of a filter according to DE 102 23 452 AI, which allows the exhaust gas back pressure to rise slightly can.
- Partial image a shows the longitudinal sectional side view of the alternative support structure 26 with openings of the expanded metal lattice that are only partially filled with sintered metal, in which the fiber layer S has a corrugated surface 51 on the side facing away from the sintered metal.
- the mountains of the waveform lie above the webs of the Expanded metal grid, while the valleys of the waveform are arranged in the areas in between.
- the wave-shaped application increases the surface of the fiber layer compared to a flat application.
- Partial image b shows a corresponding arrangement of a fiber layer S with a corrugated surface 51, which is applied to the further alternative support structure 35 according to FIG. 3.
- FIG. 6 shows three examples of further embodiments in longitudinal sectional partial views.
- the structure according to sub-picture a comprises a load-bearing basic structure or support structure F made of expanded metal filled with sintered metal according to FIG. 2b with the thickness 24.
- a schematically illustrated fleece or a fiber mat 60 made of ceramic fibers is applied to the upstream side Soot filtration and storage is used.
- the basic material of such nonwoven fabrics known per se is a ceramic material, for example aluminum oxide.
- the thickness 65 of the fiber mat 60 is (in the final state, that is to say after attachment to the support structure F) from 0.05 to 2 millimeters, in particular 0.1 to 0.5 millimeters.
- the porosity of the fiber structure is over 70 percent, preferably above 85 percent.
- the active surface of the fibers of the fiber mat is over 1 square meter per weight gram, preferably over 30 square meters per weight gram.
- the fiber fleece is applied to the support structure in one process step after sintering the support structure F containing sintered metal.
- the fiber mat is bonded to the sintered metal surface by using an inorganic binder based on aluminum oxide or silicon oxide sols or a mixture of the two components and a subsequent thermal treatment at around 500 to 800 degrees Celsius for 30 to 60 minutes in an air atmosphere.
- the fleece is applied, for example, to the still unprocessed expanded metal-sintered metal walls.
- the fleece can be placed on the already formed filter bags before the filter is finally assembled be applied, in a further alternative to the already welded filter bags before final assembly of the filter.
- the nonwovens are introduced into the upstream spaces between the pockets and applied there to the pocket surfaces.
- the nonwoven fabric 60 is alternatively applied to a partially filled support structure 26 according to FIG. 2c, so that a corrugated surface 61 is formed on the side of the fiber layer facing the inflowing exhaust gas in a manner similar to an arrangement according to FIG. 5a.
- a corrugated surface 61 of the fiber fleece 60 (optionally mixed with catalytic material) is realized using a support structure 35 according to FIG. 3 having a sintered metal foil 30.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Toxicology (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Materials (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
- Filtering Of Dispersed Particles In Gases (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/557,783 US20070041880A1 (en) | 2003-12-20 | 2003-12-20 | Exhaust treatment device |
EP04802768A EP1715939A1 (de) | 2003-12-20 | 2004-11-19 | Abgasnachbehandlungsanordnung |
JP2006508130A JP2006525866A (ja) | 2003-12-20 | 2004-11-19 | 排ガス後処理装置 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10360254.2 | 2003-12-20 | ||
DE10360254 | 2003-12-20 | ||
DE102004053267A DE102004053267A1 (de) | 2003-12-20 | 2004-11-04 | Abgasnachbehandlungsanordnung |
DE102004053267.2 | 2004-11-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005061079A1 true WO2005061079A1 (de) | 2005-07-07 |
Family
ID=34712324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2004/002555 WO2005061079A1 (de) | 2003-12-20 | 2004-11-19 | Abgasnachbehandlungsanordnung |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070041880A1 (de) |
EP (1) | EP1715939A1 (de) |
JP (1) | JP2006525866A (de) |
KR (1) | KR20060111587A (de) |
WO (1) | WO2005061079A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2170484A1 (de) * | 2007-07-16 | 2010-04-07 | NV Bekaert SA | Filtermedium |
WO2009020835A2 (en) * | 2007-08-03 | 2009-02-12 | Errcive, Inc. | Porous bodies and methods |
US7897255B2 (en) * | 2007-09-06 | 2011-03-01 | GE02 Technologies, Inc. | Porous washcoat-bonded fiber substrate |
US20090263303A1 (en) * | 2007-10-16 | 2009-10-22 | Aspen Products Group, Inc. | Purification Device and Method for Purifying a Fluid Stream |
US8277743B1 (en) | 2009-04-08 | 2012-10-02 | Errcive, Inc. | Substrate fabrication |
US8359829B1 (en) | 2009-06-25 | 2013-01-29 | Ramberg Charles E | Powertrain controls |
US9833932B1 (en) | 2010-06-30 | 2017-12-05 | Charles E. Ramberg | Layered structures |
CN112556440A (zh) * | 2020-12-30 | 2021-03-26 | 刘露雨 | 燃煤锅炉窑炉消烟除尘脱硫脱氮技术装置 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3337903A1 (de) * | 1983-10-19 | 1985-05-09 | Werner 7101 Flein Baum | Katalysatoranordnung |
EP0288746A1 (de) * | 1987-04-29 | 1988-11-02 | Hüls Aktiengesellschaft | Plattenförmiger Katalysator zur Entfernung von Stickstoffoxiden aus Abgasen |
EP0340784A1 (de) * | 1988-05-06 | 1989-11-08 | Ente per le nuove tecnologie, l'energia e l'ambiente (ENEA) | Gerät zum Vermindern der von Verbrennungsmotorabgasen verursachten Luftverschmutzung |
WO2001019493A1 (en) * | 1999-09-10 | 2001-03-22 | N.V. Bekaert S.A. | Welded microfilter tube comprising sintered fibers |
WO2001036097A1 (fr) | 1999-11-16 | 2001-05-25 | Ibiden Co., Ltd. | Catalyseur et procede de preparation correspondant |
DE10223452A1 (de) | 2002-05-25 | 2003-12-04 | Hjs Fahrzeugtechnik Gmbh & Co | Partikelfilter für Abgase von Brennkraftmaschinen |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE789706A (fr) * | 1971-10-05 | 1973-02-01 | Johnson Matthey Co Ltd | Structure-support pour catalyseurs |
US3881877A (en) * | 1971-10-05 | 1975-05-06 | Matthey Bishop Inc | Catalyst supporting screen |
US3857688A (en) * | 1971-10-27 | 1974-12-31 | Ppg Industries Inc | Lead filter |
US3871850A (en) * | 1973-03-20 | 1975-03-18 | Ethyl Corp | Filter element |
US4195063A (en) * | 1974-09-03 | 1980-03-25 | Matsushita Electric Industrial Co., Ltd. | Catalyst element for cleaning exhaust gases |
US4255173A (en) * | 1977-12-27 | 1981-03-10 | Texaco Inc. | Lead filter for internal combustion engine exhaust gases |
US4181514A (en) * | 1978-02-14 | 1980-01-01 | Huyck Corporation | Stitch knitted filters for high temperature fluids and method of making them |
US4530418A (en) * | 1982-06-01 | 1985-07-23 | Currie Neil L | Automotive exhaust system |
IN163767B (de) * | 1985-05-29 | 1988-11-05 | Pipercross Ltd | |
DE4110285A1 (de) * | 1991-03-28 | 1992-10-01 | Schwaebische Huettenwerke Gmbh | Filter- oder katalysatorkoerper |
US5204067A (en) * | 1991-07-11 | 1993-04-20 | Schwaebische Huettenwerke Gmbh | Filter |
US5470364A (en) * | 1992-01-07 | 1995-11-28 | Pall Corporation | Regenerable diesel exhaust filter |
US5228891A (en) * | 1992-01-07 | 1993-07-20 | Pall Corporation | Regenerable diesel exhaust filter |
US5180409A (en) * | 1992-01-30 | 1993-01-19 | Minnesota Mining And Manufacturing Company | Hot-gas-filtering fabric of spaced uncrimped support strands and crimped lofty fill yarns |
DE4394868T1 (de) * | 1992-09-25 | 1994-10-20 | Toyoda Automatic Loom Works | Hitzebeständiges Filter |
US5409669A (en) * | 1993-01-25 | 1995-04-25 | Minnesota Mining And Manufacturing Company | Electrically regenerable diesel particulate filter cartridge and filter |
EP0754267B1 (de) * | 1994-04-06 | 1998-07-15 | Minnesota Mining And Manufacturing Company | Elektrisch regenerierbare dieselpartikelfilterpatrone und filter |
US5651250A (en) * | 1994-05-24 | 1997-07-29 | Isuzu Ceramics Research Institute Co., Ltd. | Diesel particulate filter apparatus |
US5611831A (en) * | 1994-11-16 | 1997-03-18 | Isuzu Ceramics Research Institute Co., Ltd. | Diesel particulate filter apparatus |
US5682740A (en) * | 1995-05-12 | 1997-11-04 | Isuzu Ceramics Research Institute Co., Ltd. | Diesel particulate filter apparatus |
JPH09217618A (ja) * | 1996-02-09 | 1997-08-19 | Isuzu Ceramics Kenkyusho:Kk | 排気ガス浄化装置 |
US5780126A (en) * | 1996-07-17 | 1998-07-14 | Minnesota Mining & Manufacturing | Filter material |
US6159258A (en) * | 1998-11-30 | 2000-12-12 | Dana Corporation | Air filter elements with foam pre-cleaners |
JP3445775B2 (ja) * | 2000-02-22 | 2003-09-08 | トヨタ自動車株式会社 | パティキュレート・フィルタ |
JP3921927B2 (ja) * | 2000-07-25 | 2007-05-30 | いすゞ自動車株式会社 | デイーゼル機関の排気微粒子除去フイルタ |
FR2821281B1 (fr) * | 2001-02-28 | 2003-04-18 | Inst Francais Du Petrole | Separateur en matiere poreuse comprenant une structure en feutre et appareil comprenant un tel separateur |
BR0209626A (pt) * | 2001-06-18 | 2004-03-23 | Hjs Fahrzeugtechnik Gmbh & Co | Filtro de partìculas de gás de escape de metal sinterado |
AU2003302247A1 (en) * | 2002-12-12 | 2004-07-09 | Mykrolis Corporation | Porous sintered composite materials |
DE102005033635A1 (de) * | 2005-07-19 | 2007-01-25 | Robert Bosch Gmbh | Vorrichtung zur Reinigung von Gasgemischen und Verfahren zu deren Herstellung |
-
2003
- 2003-12-20 US US10/557,783 patent/US20070041880A1/en not_active Abandoned
-
2004
- 2004-11-19 EP EP04802768A patent/EP1715939A1/de not_active Withdrawn
- 2004-11-19 WO PCT/DE2004/002555 patent/WO2005061079A1/de active Application Filing
- 2004-11-19 KR KR1020067012105A patent/KR20060111587A/ko not_active Application Discontinuation
- 2004-11-19 JP JP2006508130A patent/JP2006525866A/ja not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3337903A1 (de) * | 1983-10-19 | 1985-05-09 | Werner 7101 Flein Baum | Katalysatoranordnung |
EP0288746A1 (de) * | 1987-04-29 | 1988-11-02 | Hüls Aktiengesellschaft | Plattenförmiger Katalysator zur Entfernung von Stickstoffoxiden aus Abgasen |
EP0340784A1 (de) * | 1988-05-06 | 1989-11-08 | Ente per le nuove tecnologie, l'energia e l'ambiente (ENEA) | Gerät zum Vermindern der von Verbrennungsmotorabgasen verursachten Luftverschmutzung |
WO2001019493A1 (en) * | 1999-09-10 | 2001-03-22 | N.V. Bekaert S.A. | Welded microfilter tube comprising sintered fibers |
WO2001036097A1 (fr) | 1999-11-16 | 2001-05-25 | Ibiden Co., Ltd. | Catalyseur et procede de preparation correspondant |
DE10223452A1 (de) | 2002-05-25 | 2003-12-04 | Hjs Fahrzeugtechnik Gmbh & Co | Partikelfilter für Abgase von Brennkraftmaschinen |
Also Published As
Publication number | Publication date |
---|---|
EP1715939A1 (de) | 2006-11-02 |
JP2006525866A (ja) | 2006-11-16 |
KR20060111587A (ko) | 2006-10-27 |
US20070041880A1 (en) | 2007-02-22 |
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