US20170284248A1 - Particle filter and method for producing a particle filter - Google Patents
Particle filter and method for producing a particle filter Download PDFInfo
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- US20170284248A1 US20170284248A1 US15/509,399 US201515509399A US2017284248A1 US 20170284248 A1 US20170284248 A1 US 20170284248A1 US 201515509399 A US201515509399 A US 201515509399A US 2017284248 A1 US2017284248 A1 US 2017284248A1
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- Prior art keywords
- particle filter
- catalytic activity
- face
- exhaust gas
- coating
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Classifications
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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
- F01N3/033—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 in combination with other devices
- F01N3/035—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 in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
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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
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
- F01N13/0093—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are of the same type
-
- 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
- F01N3/18—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 methods of operation; Control
- F01N3/20—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 methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
-
- 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
- F01N2250/00—Combinations of different methods of purification
- F01N2250/02—Combinations of different methods of purification filtering and catalytic conversion
-
- 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
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
-
- 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
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
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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
-
- 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 relates to a particle filter and a process for producing a particle filter.
- the particle filter is used, in particular, as exhaust gas treatment unit in an exhaust gas system, preferably in an exhaust gas system of a diesel internal combustion engine of a motor vehicle.
- Particle filters of this type are formed from a porous, optionally extruded, structure, for example of the honeycomb structure type.
- the shape of this honeycomb structure is not subject to any particular restrictions. However, a circle, an ellipse or an oval, for example, can serve as outer cross-sectional shape of the honeycomb structure.
- the cross-sectional shape of the flow channels is likewise not subject to any restrictions, but an angular cross-sectional shape is normally preferred, for example of the type of a triangle, a quadrilateral, a hexagon or the like.
- the cell density for the flow channels can likewise be varied within wide limits, and preference is given, for example, to the shape having a flow channel density in the range from 50 to 400 cells per square inch (7.8 to 62 cells per square centimeter).
- the porous channel walls can, for example, be formed by ceramic. Silicon carbide or metal-silicon, and silicon carbide, for example, have been found to be suitable. If the ceramic has a metal-silicon and silicon carbide as main crystal phase, the Si content defined by Si (Si+SIC) is preferably from 5 to 50% by mass, preferably from 10 to 40% by mass.
- Such particle filters are normally referred to as “wall-flow filters” because they force at least a major part of the exhaust gas stream through the porous channel walls.
- wall-flow filters alternate closure of the adjacent flow channels of the particle filter at the two end faces is known.
- a “closure” can also be configured with a significantly smaller passage opening compared to the channel cross section, in particular in the case of selected or all channels, at the second (exhaust gas outflow end) end face, so that a bypass is made possible (and thus blocking of the particle filter when correct flow cannot occur through the channel wall as a result of the particle loading).
- a substream of the exhaust gas thus flows into a first flow channel, which is open at the exhaust gas outflow end and is forced by the closure at the end of this flow channel to flow (at least mostly during normal operation of the particle filter) through the porous channel wall into an adjacent flow channel and flow out through this open end on the exhaust gas exit side.
- particles entrained in the exhaust gas can also be embedded and optionally reduced or converted into gaseous constituents.
- Such particle filters having porous walls normally have a particularly large internal surface area, so that a very large catalytically active area can be provided here for a corresponding coating in a relatively small construction volume. For this reason, the use of such particle filters has been proposed as preferred, also in combination with an SCR system.
- SCR selective catalytic reduction
- the nitrogen oxides (NO, NO 2 ) are preferentially reduced while undesirable secondary reactions (e.g., the oxidation of sulfur oxide to sulfur trioxide) are largely suppressed.
- ammonia (NH 3 ) is normally used as a reducing agent that is mixed into the exhaust gas.
- the products of the reaction are water (H 2 O) and nitrogen (N 2 ).
- Suitable catalysts employed are, for example, titanium dioxide, vanadium pentoxide and/or tungsten oxide.
- the use of zeolites is also possible.
- the SCR process is used particularly in diesel vehicles, especially in commercial vehicles, in order to decrease the pollutant emissions in respect of nitrogen oxide pollution.
- a particle filter that provides advantages with respect to complete conversion of the SCR reactions or the hydrolysis of added reducing agent possible in SCR systems in particular is provided.
- a process for producing such particle filters is proposed, so that reliable and inexpensive production is made possible.
- a particle filter for an exhaust gas system in particular for a motor vehicle having a diesel internal combustion engine, is provided.
- the particle filter comprises a plurality of flow channels extending from a first end face through to a second end face and being separated from one another by porous channel walls.
- the flow channels each have a closure alternately at the end faces so that an exhaust gas enters a flow channel open at the first end face, flows through the channel wall and flows out from the particle filter through an adjacent flow channel open at the second end face.
- the channel wall has at least the following layers in succession in a flow direction of the exhaust gas:
- the particle filter layer serves, in particular, to filter solid particles (soot or the like) out of the exhaust gas stream. These particles are held back by the small pores in the particle filter layer, so that a major part of the particles, preferably at least 80% by mass, cannot pass through into the intermediate layer.
- the particle filter layer can be regenerated at time intervals that can be determined freely or continuously (CRT), so that particles are converted by NO 2 present in the exhaust gas or by thermal oxidation.
- the particle filter layer additionally comprises a hydrolysis coating, so that a reducing agent precursor (e.g., urea/water solution) added upstream of the particle filter is at least partly converted into a reducing agent (e.g., ammonia) during passage through the particle filter layer.
- a reducing agent precursor e.g., urea/water solution
- a reducing agent e.g., ammonia
- the particle filter layer is, in particular, applied in the form of a coating to the exhaust gas entry side of the porous channel walls, so that there is a sharp separation between the particle filter layer and the intermediate layer.
- the particle filter layer consists, in particular, at least of a
- the thickness of the particle filter layer is, in particular, from 30 to 150 ⁇ m, preferably from 50 to 100 ⁇ m.
- the intermediate layer arranged downstream of the particle filter layer has a first SCR coating having a first activity.
- the first activity of the first SCR coating in the intermediate layer can also be indicated by a density of the catalytically active material or by the average distance between catalytically active sites.
- the particle filter has a porous channel wall which consists, at least in the region of the intermediate layer before a coating with the first SCR coating, exclusively of a ceramic base material (see introduction). Only in a coating step carried out separately is the first SCR coating applied, so that the above-described properties of the intermediate layer in respect of porosity and pore size are then present.
- the thickness of the intermediate layer is from 200 to 500 ⁇ m, preferably from 200 to 400 ⁇ m.
- the particle filter additionally has a second SCR coating on the side of the intermediate layer opposite the particle filter layer, where the second catalytic activity is different from, the first catalytic activity, i.e., in terms of the respective density or type of the catalytically active material or the respective average distance between catalytically active sites.
- the catalytic activity of the first and second SCR coatings is set via the proportion of the catalytically active materials in the coating, i.e., for example, titanium dioxides tungsten dioxide, vanadium pentoxide or zeolite.
- the thickness of the second SCR coating is from 10 to 200 ⁇ m, preferably from 10 to 50 ⁇ m.
- the arrangement of the particle filter layer upstream of the intermediate layer and upstream of the second SCR coating ensures that soot particles can be converted by NO 2 present in the exhaust gas.
- the NO 2 present in the exhaust gas is thus available, especially at low temperatures, exclusively for the conversion of soot particles.
- Only after flowing through the particle filter layer is NO 2 (and other NO x compounds) converted in the SCR-coated intermediate layer and in the second SCR coating according to the following reactions:
- the first SCR coating in the intermediate layer has a lower first catalytic activity than the second catalytic activity of the second SCR coating.
- the porous intermediate layer makes it possible for nitrogen oxides to be temporarily stored and gradually released again into the exhaust gas stream.
- the second SCR coating arranged downstream of the intermediate layer ensures, in particular in the case of a relatively high catalytic activity that a virtually complete conversion of the nitrogen oxides occurs.
- the multistage coating of the particle filter makes it possible for a separation of particle deposition and particle conversion, on the one hand, and nitrogen oxide reduction, on the other hand, to be ensured.
- the NO 2 present in the exhaust gas can be utilized effectively for the continuous regeneration of the particle filter, with the further conversion of the nitrogen oxides then still, present occurring directly downstream of the particle filter layer in the same channel wall of the particle filter.
- particle filter and SCR catalyst optionally also hydrolysis catalyst
- hydrolysis catalyst can be created, with large surface areas being simultaneously provided for particle attachment and catalytic conversion.
- the e.g., ceramic porous channel wall of a conventional particle filter can now be used simultaneously for hydrolysis, particle filtration and nitrogen oxide temporary storage/conversion.
- the required SCR activity and temporary storage capacity can be set precisely by the different first and second SCR coatings, so that effective utilization of the catalytically active materials is possible.
- a process for producing a particle filter in particular for producing a particle filter according to the invention, is proposed.
- the process comprises at least the following steps:
- a particle filter having a plurality of flow channels extending from a first end face to a second end face and being separated from one another by porous channel walls;
- a particle filter layer on channel walls of the flow channels that are open at the first end face, where the particle filter layer has a porosity of from 5 to 50% and an average pore size of from 5 to 15 ⁇ m [micron], preferably from 5 to 10 ⁇ m.
- the information given in respect of the particle filter is also applicable to the process and vice versa. This applies particularly for information regarding the particle filter layer, the first and second SCR coatings and the intermediate layer.
- At least the channel walls as per step a) and the particle filter layer as per step a) are produced by a printing process.
- a printing process it is possible to use a three-dimensional printing process by which a particle filter and, in particular, the channel walls can be produced in layers.
- a printing process also enables the different properties of the individual layers (particle filter layer, intermediate layer) to be separated sharply from one another.
- the particle filter layer as per step e) is applied by a coating process.
- the closures as per step b) are arranged before the step e), so that coating can be carried out via the exhaust gas entry end of the particle filter, via the channels of the particle filter which are open at the exhaust gas entry end.
- the particle filter layer as per step e) is applied at least after step c). It can in this way be ensured that catalytically active materials of the first SCR coating do not penetrate into the particle filter layer. A sharp separation of first SCR coating and particle filter layer is thus possible.
- the second catalytic activity of the second SCR coating is greater than the first, catalytic activity of the first SCR coating.
- first SCR coating used for step c) has a first viscosity and the second SCR coating used for step d) has a second viscosity, where: first viscosity ⁇ second viscosity.
- the low viscosity of the first SCR coating allows uniform, and permeating, coating of the intermediate layer, i.e., of the porous channel wall, with catalytically active materials.
- the higher viscosity of the second SCR coating ensures that the second SCR coating does not mix with the first SCR coating, or covers the latter in the pores of the intermediate layer. In particular, it is ensured in this way that even here, between first and second SCR coatings, there is a sharp spatial separation.
- the second SCR coating is thus applied only to the exhaust gas exit side of the porous channel walls, with the second SCR coating not penetrating, in particular, into the intermediate layer, or into the porous channel wall.
- the invention is also directed to a motor vehicle having an internal combustion engine and an exhaust gas system, wherein the exhaust gas system comprises a particle filter according to the invention or a particle filter produced by the process of the invention.
- FIG. 1 shows a motor vehicle having an exhaust gas system
- FIG. 2 shows a section of a particle filter
- FIG. 3 shows a detail of FIG. 2 ;
- FIG. 4 shows a process step a
- FIG. 5 shows a process step b
- FIG. 6 shows a process step c
- FIG. 7 shows a process step d
- FIG. 8 shows a process step e).
- FIG. 1 shows a motor vehicle 3 having an internal combustion engine 4 and an exhaust gas system 2 .
- the exhaust gas system 2 comprises an addition unit 22 for a reducing agent or a reducing agent precursor, which can be taken from a tank 23 .
- a particle filter 1 is arranged downstream of the addition unit 22 .
- An exhaust gas 10 flows through the exhaust gas system 2 from the internal combustion engine through to the particular filter The exhaust gas 10 enters the particle filter 1 via a first end face 6 and leaves it again via a second end face 7 .
- FIG. 2 shows a section of the particle filter 1 as shown in FIG. 1 .
- the particle filter comprises a plurality of flow channels 5 which extend, parallel to one another and separated from one another by porous channel walls 8 , from the first end face 6 to the second end face 7 .
- Closures 9 are arranged alternately in the flow channels 5 at the end faces 6 and 7 .
- the exhaust gas 10 enters the open flow channels 5 via the first end face 6 and is forced by closure 9 to flow through the channel walls 8 in the flow direction 11 .
- the flow channels 5 which are open at the first, end face 6 form the exhaust gas entry side 12
- the flow channels 5 which are open at the second end face 7 form the exhaust gas exit side 17 .
- FIG. 3 shows a detail III of FIG. 2 .
- a channel wall 8 extends from the first end face 6 through to the second end face 7 .
- An exhaust gas 10 flows in the flow direction 11 through the porous channel wall 8 .
- a particle filter layer 13 is arranged on the channel wall 8 on the exhaust gas entry side 12 . Downstream of the particle filter layer 13 , an intermediate layer 14 which comprises a first SCR coating 15 having a first catalytic activity 16 is present in the porous channel wall 8 . Downstream of the intermediate layer 14 , on the exhaust gas exit, side 17 of the channel wall 8 , there is a second SCR coating 18 having a second catalytic activity 19 .
- FIG. 4 shows process step a), i.e., the still uncoated channel walls B that form the flow channels 5 .
- FIG. 5 shows process step b), in which closures 9 are arranged alternately, so that the flow direction 11 is then prescribed by the channel walls 8 .
- FIG. 8 shows process step c), in which the porous channel wall 8 is provided with a first SCR coating 15 f which has a first viscosity 20 , so as to form an intermediate layer 14 .
- This process step can, in particular, also be carried out before process step b).
- FIG. 7 shows process step d), in which the second SCR coating 18 , which has a second viscosity 21 , is arranged on the intermediate layer 14 on the exhaust gas exit side 1 of the channel wall 8 ,
- the second viscosity 21 is greater than the first viscosity 20 of the first SCR coating 15 , so that it is not possible for the second SCR coating 18 to penetrate into the intermediate layer 14 .
- FIG. 8 shows process step e), in which the particle filter layer 13 is arranged on the intermediate layer 14 on the exhaust gas entry side 12 of the channel wall 8 .
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Materials (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a particle filter (1) for an exhaust gas system (2), and to a method for producing a particle filter. The particle filter (1) comprises a plurality of flow channels (5), which extend from a first end face (6) towards a second end face (7) and which are separated from one another by porous channel walls (8). On the end faces (6, 7), the flow channels (5) each have mutual closing means (9) such that an exhaust gas (10) enters a flow channel (5) that is open on the first end face (6), flows through the channel wall (8), and escapes from the particle filter (1) by way of an adjacent flow channel (5) that is open on the second end face (7). In a direction of flow (11), the channel wall (8) has, in succession, the following layers: a particle filter layer (13); an intermediate layer (14) comprising a first SCR coating (15) having a first catalytic activity (16); a second SCR coating (18) having a second catalytic activity (19), wherein the second catalytic activity (19) is different from the first catalytic activity (16).
Description
- This is a U.S. national stage of application No. PCT/EP2015/070387, filed on 7 Sep. 2015, which claims priority to the German Application No. 10 2014 112 862,1 filed 8 Sep. 2014, the content of both incorporated herein by reference.
- The invention relates to a particle filter and a process for producing a particle filter. The particle filter is used, in particular, as exhaust gas treatment unit in an exhaust gas system, preferably in an exhaust gas system of a diesel internal combustion engine of a motor vehicle.
- Particle filters of this type are formed from a porous, optionally extruded, structure, for example of the honeycomb structure type. The shape of this honeycomb structure is not subject to any particular restrictions. However, a circle, an ellipse or an oval, for example, can serve as outer cross-sectional shape of the honeycomb structure. The cross-sectional shape of the flow channels is likewise not subject to any restrictions, but an angular cross-sectional shape is normally preferred, for example of the type of a triangle, a quadrilateral, a hexagon or the like. The cell density for the flow channels can likewise be varied within wide limits, and preference is given, for example, to the shape having a flow channel density in the range from 50 to 400 cells per square inch (7.8 to 62 cells per square centimeter). The porous channel walls can, for example, be formed by ceramic. Silicon carbide or metal-silicon, and silicon carbide, for example, have been found to be suitable. If the ceramic has a metal-silicon and silicon carbide as main crystal phase, the Si content defined by Si (Si+SIC) is preferably from 5 to 50% by mass, preferably from 10 to 40% by mass.
- Such particle filters are normally referred to as “wall-flow filters” because they force at least a major part of the exhaust gas stream through the porous channel walls. For this purpose, alternate closure of the adjacent flow channels of the particle filter at the two end faces is known. A “closure” can also be configured with a significantly smaller passage opening compared to the channel cross section, in particular in the case of selected or all channels, at the second (exhaust gas outflow end) end face, so that a bypass is made possible (and thus blocking of the particle filter when correct flow cannot occur through the channel wall as a result of the particle loading). A substream of the exhaust gas thus flows into a first flow channel, which is open at the exhaust gas outflow end and is forced by the closure at the end of this flow channel to flow (at least mostly during normal operation of the particle filter) through the porous channel wall into an adjacent flow channel and flow out through this open end on the exhaust gas exit side. During flow through the porous channel walls, particles entrained in the exhaust gas can also be embedded and optionally reduced or converted into gaseous constituents.
- Such particle filters having porous walls normally have a particularly large internal surface area, so that a very large catalytically active area can be provided here for a corresponding coating in a relatively small construction volume. For this reason, the use of such particle filters has been proposed as preferred, also in combination with an SCR system. In selective catalytic reduction (SCR), the nitrogen oxides (NO, NO2) are preferentially reduced while undesirable secondary reactions (e.g., the oxidation of sulfur oxide to sulfur trioxide) are largely suppressed. For this reaction to proceed, ammonia (NH3) is normally used as a reducing agent that is mixed into the exhaust gas. The products of the reaction are water (H2O) and nitrogen (N2). Suitable catalysts employed are, for example, titanium dioxide, vanadium pentoxide and/or tungsten oxide. The use of zeolites is also possible. The SCR process is used particularly in diesel vehicles, especially in commercial vehicles, in order to decrease the pollutant emissions in respect of nitrogen oxide pollution.
- The systems proposed hitherto for firstly particle reduction and secondly nitrogen oxide reduction sometimes have a very complex structure and require a large amount of construction space. In addition, it is necessary in the case of some systems for complicated conditioning of the reducing agent, for example urea or the like, to be carried out externally to the exhaust gas and/or in the exhaust gas system itself, and complete conversion can sometimes not be ensured. For this reason, provision of a barrier catalyst intended to prevent breakthrough of nitrogen oxides in the event of insufficient conversion of the reducing agent has frequently also been proposed.
- In view of the problems of the prior art discussed above, it is an object of the present invention to at least partly solve these problems of the prior art. In particular, in one aspect, a particle filter that provides advantages with respect to complete conversion of the SCR reactions or the hydrolysis of added reducing agent possible in SCR systems in particular is provided. In addition, a process for producing such particle filters is proposed, so that reliable and inexpensive production is made possible.
- These objects are achieved by a particle filter and by a process for producing a particle filter. In particular, the process serves to produce the particle filter of the invention. The features safe forth individually can be combined with one another in any technologically purposeful way and can be supplemented by explanatory subject matter from the description, with further variants of the invention being indicated.
- According to a first aspect of the present invention a particle filter for an exhaust gas system, in particular for a motor vehicle having a diesel internal combustion engine, is provided. The particle filter comprises a plurality of flow channels extending from a first end face through to a second end face and being separated from one another by porous channel walls. The flow channels each have a closure alternately at the end faces so that an exhaust gas enters a flow channel open at the first end face, flows through the channel wall and flows out from the particle filter through an adjacent flow channel open at the second end face. The channel wall has at least the following layers in succession in a flow direction of the exhaust gas:
-
- a particle filter layer having a porosity of from 60 to 90%, preferably from 80 to 90%, and an average pore size of from 2 to 10 μm [micron], preferably from 3 to 5 μm on the exhaust gas entry side;
- an intermediate layer having a porosity of from 40 to 60%, preferably from 50 to 60%, and an average pore size of from 10 to 20 μm [micron] , preferably from 14 to 16 μm, where the intermediate layer comprises a first SCR coating having a first catalytic activity;
- a second SCR coating having a second catalytic activity, where the second catalytic activity is different from the first catalytic activity, on the exhaust gas exit side.
- The particle filter layer serves, in particular, to filter solid particles (soot or the like) out of the exhaust gas stream. These particles are held back by the small pores in the particle filter layer, so that a major part of the particles, preferably at least 80% by mass, cannot pass through into the intermediate layer. The particle filter layer can be regenerated at time intervals that can be determined freely or continuously (CRT), so that particles are converted by NO2 present in the exhaust gas or by thermal oxidation.
- In particular, in another aspect the particle filter layer additionally comprises a hydrolysis coating, so that a reducing agent precursor (e.g., urea/water solution) added upstream of the particle filter is at least partly converted into a reducing agent (e.g., ammonia) during passage through the particle filter layer.
- In another aspect, the particle filter layer is, in particular, applied in the form of a coating to the exhaust gas entry side of the porous channel walls, so that there is a sharp separation between the particle filter layer and the intermediate layer. The particle filter layer consists, in particular, at least of a
-
- washcoat (Al2O3),
- which optionally additionally comprises a hydrolysis coating, wherein the hydrolysis coating comprises, in particular,
- titanium dioxide or
- titanium oxide-supported tungsten dioxide catalysts and vanadium-tungsten oxide catalysts.
- In another aspect, the thickness of the particle filter layer is, in particular, from 30 to 150 μm, preferably from 50 to 100 μm.
- In another aspect, the intermediate layer arranged downstream of the particle filter layer has a first SCR coating having a first activity. The first activity of the first SCR coating in the intermediate layer can also be indicated by a density of the catalytically active material or by the average distance between catalytically active sites.
- In particular, in another aspect, the particle filter has a porous channel wall which consists, at least in the region of the intermediate layer before a coating with the first SCR coating, exclusively of a ceramic base material (see introduction). Only in a coating step carried out separately is the first SCR coating applied, so that the above-described properties of the intermediate layer in respect of porosity and pore size are then present.
- In particular,, the thickness of the intermediate layer is from 200 to 500 μm, preferably from 200 to 400 μm.
- In another aspect, the particle filter additionally has a second SCR coating on the side of the intermediate layer opposite the particle filter layer, where the second catalytic activity is different from, the first catalytic activity, i.e., in terms of the respective density or type of the catalytically active material or the respective average distance between catalytically active sites.
- In particular, the catalytic activity of the first and second SCR coatings is set via the proportion of the catalytically active materials in the coating, i.e., for example, titanium dioxides tungsten dioxide, vanadium pentoxide or zeolite.
- In particular, the thickness of the second SCR coating is from 10 to 200 μm, preferably from 10 to 50 μm.
- The arrangement of the particle filter layer upstream of the intermediate layer and upstream of the second SCR coating ensures that soot particles can be converted by NO2 present in the exhaust gas. The NO2 present in the exhaust gas is thus available, especially at low temperatures, exclusively for the conversion of soot particles. Only after flowing through the particle filter layer is NO2 (and other NOx compounds) converted in the SCR-coated intermediate layer and in the second SCR coating according to the following reactions:
-
4NH3+4NO+O2→4N2+6H2O (“Standard SCR”) -
2NH3+NO+NO2→2N2+3H2O (“Fast SCR”) -
4NH3+3NO2→3.5N2+6H2O (“NO2 SCR”) - In particular, the first SCR coating in the intermediate layer has a lower first catalytic activity than the second catalytic activity of the second SCR coating.
- In particular, the porous intermediate layer makes it possible for nitrogen oxides to be temporarily stored and gradually released again into the exhaust gas stream. The second SCR coating arranged downstream of the intermediate layer ensures, in particular in the case of a relatively high catalytic activity that a virtually complete conversion of the nitrogen oxides occurs. The multistage coating of the particle filter makes it possible for a separation of particle deposition and particle conversion, on the one hand, and nitrogen oxide reduction, on the other hand, to be ensured. Thus, the NO2 present in the exhaust gas can be utilized effectively for the continuous regeneration of the particle filter, with the further conversion of the nitrogen oxides then still, present occurring directly downstream of the particle filter layer in the same channel wall of the particle filter. Furthermore, a space-saving arrangement of particle filter and SCR catalyst, optionally also hydrolysis catalyst, can be created, with large surface areas being simultaneously provided for particle attachment and catalytic conversion. In addition, the e.g., ceramic porous channel wall of a conventional particle filter can now be used simultaneously for hydrolysis, particle filtration and nitrogen oxide temporary storage/conversion. The required SCR activity and temporary storage capacity can be set precisely by the different first and second SCR coatings, so that effective utilization of the catalytically active materials is possible.
- In another aspect, a process for producing a particle filter, in particular for producing a particle filter according to the invention, is proposed. The process comprises at least the following steps:
- a) provision of a particle filter having a plurality of flow channels extending from a first end face to a second end face and being separated from one another by porous channel walls;
- b) alternate arrangement of closures in the flow channels at the end faces;
- c) coating of the porous channel wall with a first SCR coating that has a first catalytic activity;
- d) coating of the channel walls of the flow channels that are open at the second end face with a second SCR coating having a second catalytic activity, where the second catalytic activity is different from the first catalytic activity;
- e) arrangement of a particle filter layer on channel walls of the flow channels that are open at the first end face, where the particle filter layer has a porosity of from 5 to 50% and an average pore size of from 5 to 15 μm [micron], preferably from 5 to 10 μm.
- It is expressly pointed out that the information given in respect of the particle filter is also applicable to the process and vice versa. This applies particularly for information regarding the particle filter layer, the first and second SCR coatings and the intermediate layer.
- In a preferred configuration, at least the channel walls as per step a) and the particle filter layer as per step a) are produced by a printing process. In particular, it is possible to use a three-dimensional printing process by which a particle filter and, in particular, the channel walls can be produced in layers. A printing process also enables the different properties of the individual layers (particle filter layer, intermediate layer) to be separated sharply from one another.
- In an advantageous embodiment, the particle filter layer as per step e) is applied by a coating process. In particular, the closures as per step b) are arranged before the step e), so that coating can be carried out via the exhaust gas entry end of the particle filter, via the channels of the particle filter which are open at the exhaust gas entry end.
- In particular, the particle filter layer as per step e) is applied at least after step c). It can in this way be ensured that catalytically active materials of the first SCR coating do not penetrate into the particle filter layer. A sharp separation of first SCR coating and particle filter layer is thus possible.
- In particular, the second catalytic activity of the second SCR coating is greater than the first, catalytic activity of the first SCR coating.
- In particular, the first SCR coating used for step c) has a first viscosity and the second SCR coating used for step d) has a second viscosity, where: first viscosity<second viscosity.
- The low viscosity of the first SCR coating allows uniform, and permeating, coating of the intermediate layer, i.e., of the porous channel wall, with catalytically active materials. The higher viscosity of the second SCR coating ensures that the second SCR coating does not mix with the first SCR coating, or covers the latter in the pores of the intermediate layer. In particular, it is ensured in this way that even here, between first and second SCR coatings, there is a sharp spatial separation. In particular, the second SCR coating is thus applied only to the exhaust gas exit side of the porous channel walls, with the second SCR coating not penetrating, in particular, into the intermediate layer, or into the porous channel wall. The invention is also directed to a motor vehicle having an internal combustion engine and an exhaust gas system, wherein the exhaust gas system comprises a particle filter according to the invention or a particle filter produced by the process of the invention.
- The invention and also the wide technical field are explained in more detail below with reference to the figures. It may be pointed out that the figures and in particular the size ratios depicted in the figures are purely schematic. In the drawings:
-
FIG. 1 : shows a motor vehicle having an exhaust gas system; -
FIG. 2 : shows a section of a particle filter; -
FIG. 3 : shows a detail ofFIG. 2 ; -
FIG. 4 : shows a process step a); -
FIG. 5 : shows a process step b); -
FIG. 6 : shows a process step c); -
FIG. 7 : shows a process step d); and -
FIG. 8 : shows a process step e). -
FIG. 1 shows amotor vehicle 3 having aninternal combustion engine 4 and anexhaust gas system 2. Theexhaust gas system 2 comprises anaddition unit 22 for a reducing agent or a reducing agent precursor, which can be taken from atank 23. Aparticle filter 1 is arranged downstream of theaddition unit 22. Anexhaust gas 10 flows through theexhaust gas system 2 from the internal combustion engine through to the particular filter Theexhaust gas 10 enters theparticle filter 1 via afirst end face 6 and leaves it again via a second end face 7. -
FIG. 2 shows a section of theparticle filter 1 as shown inFIG. 1 . The particle filter comprises a plurality offlow channels 5 which extend, parallel to one another and separated from one another byporous channel walls 8, from thefirst end face 6 to the second end face 7.Closures 9 are arranged alternately in theflow channels 5 at the end faces 6 and 7. Theexhaust gas 10 enters theopen flow channels 5 via thefirst end face 6 and is forced byclosure 9 to flow through thechannel walls 8 in theflow direction 11. Thus, theflow channels 5, which are open at the first,end face 6 form the exhaustgas entry side 12 and theflow channels 5, which are open at the second end face 7 form the exhaustgas exit side 17. -
FIG. 3 shows a detail III ofFIG. 2 . Achannel wall 8 extends from thefirst end face 6 through to the second end face 7. Anexhaust gas 10 flows in theflow direction 11 through theporous channel wall 8. Aparticle filter layer 13 is arranged on thechannel wall 8 on the exhaustgas entry side 12. Downstream of theparticle filter layer 13, anintermediate layer 14 which comprises afirst SCR coating 15 having a firstcatalytic activity 16 is present in theporous channel wall 8. Downstream of theintermediate layer 14, on the exhaust gas exit,side 17 of thechannel wall 8, there is asecond SCR coating 18 having a secondcatalytic activity 19. - It can be seen in
FIG. 3 that thesecond SCR coating 18 has been applied only after arrangement of theclosures 9 and that theparticle filter layer 13 has been applied before arrangement of theclosures 9. -
Particle filter layer 13,intermediate layer 14 andsecond SCR coating 18, each havingdifferent thicknesses 24, form thechannel wall 8 in thefinished particle filter 1. -
FIG. 4 shows process step a), i.e., the still uncoated channel walls B that form theflow channels 5. -
FIG. 5 shows process step b), in whichclosures 9 are arranged alternately, so that theflow direction 11 is then prescribed by thechannel walls 8. -
FIG. 8 shows process step c), in which theporous channel wall 8 is provided with a first SCR coating 15 f which has afirst viscosity 20, so as to form anintermediate layer 14. This process step can, in particular, also be carried out before process step b). -
FIG. 7 shows process step d), in which thesecond SCR coating 18, which has asecond viscosity 21, is arranged on theintermediate layer 14 on the exhaustgas exit side 1 of thechannel wall 8, Thesecond viscosity 21 is greater than thefirst viscosity 20 of thefirst SCR coating 15, so that it is not possible for thesecond SCR coating 18 to penetrate into theintermediate layer 14. -
FIG. 8 shows process step e), in which theparticle filter layer 13 is arranged on theintermediate layer 14 on the exhaustgas entry side 12 of thechannel wall 8. - It may be pointed out as a precaution that the combinations of technical features shown in the figures are not absolutely necessary in general. Thus, technical features of one figure can be combined with other technical features of a further figure and/or of the general description. Anything different only applies when the combination of features has been explicitly stated here and/or a person skilled in the art sees that the basic functions of the apparatus/of the process otherwise can no longer be performed.
- Thus, while there have been shown and described and pointed out fundamental novel features of the invention as applied to a preferred embodiment thereof, it will be understood that various omissions and substitutions and changes in the form and details of the devices illustrated, and in their operation, may be made by those skilled in the art without departing from the spirit of the invention. For example, it is expressly intended that all combinations of those elements and/or method steps which perform substantially the same function in substantially the same way to achieve the same results are within the scope of the invention. Moreover, it should be recognized that structures and/or elements and/or method steps shown and/or described, in connection with any disclosed form or embodiment of the invention may be incorporated in any other disclosed or described or suggested form or embodiment as a general matter of design choice. It is the intention, therefore, to be limited only as indicated, by the scope of the claims appended hereto.
-
- 1 Particle Filter
- 2 Exhaust gas system
- 3 Motor vehicle
- 4 Internal combustion engine
- 5 Flow channel
- 6 First end face
- 7 Second end face
- 8 Channel wall
- 9 Closure
- 10 Exhaust gas
- 11 Flow direction
- 12 Exhaust gas entry side
- 13 Particle filter layer
- 14 Intermediate layer
- 15 First SCR coating
- 16 First catalytic activity
- 17 Exhaust gas exit side
- 18 Second SCR coating
- 19 Second catalytic activity
- 20 First viscosity
- 21 Second viscosity
- 22 Addition unit
- 23 Tank
- 24 Thickness
Claims (9)
1-9. (canceled)
10. A particle filter (1) for an exhaust gas system (2), the particle filter (1) comprising:
a first end face (6);
a second end face (7);
a plurality of porous channel walls (8); and
a plurality of Sow channels (5) extending from the first end face (6), at which an exhaust gas (10) enters, through to the second end face (7), the flow channels (5) being separated from one another by respective ones of the porous channel walls (8), the flow channels (5) each having a closure (9) arranged alternately at the first and second end laces (6, 7) so that the exhaust gas (10) entering a flow channel (5) that is open at the first end face (6) flows through the channel wall (8) and flows out from the particle filter (1) through an adjacent flow channel (5) that is open at the second end face (7), each channel wall (8) having at least the following layers in succession in a flow direction (11):
a particle filter layer (13) having a porosity of from 5 to 50% and an average pore size, of from 5 to 15 μm on the exhaust gas entry side (12);
an intermediate layer (14) having a porosity of from 55 to 95% and an average pore size of from 15 to 100 μm, the intermediate layer (14) comprising a first selective catalytic reduction (SCR) coating (15) having a first catalytic activity (16); and
a second SCR coating (18) having a second catalytic activity (19), different from the first catalytic activity (16), arranged on an exhaust gas exit side (17).
11. The particle filter (1) as claimed in claim 10 , wherein the second catalytic activity (19) is greater than the first catalytic activity (16).
12. A process for producing a particle filter (1), the process comprising:
providing a plurality of flow channels (5) each extending from a first end face (6) to a second end face (7) and being separated from one another by porous channel walls (8);
alternately arranging closures (9) in the flow channels (5) at the first and second end faces (6, 7);
coating the porous channel wall (8) with a first selective catalytic reduction (SCR) coating (15) having a first catalytic activity (16);
coating the channel walls (8) of the flow channels (5) that are open at the second end face (7) with a second SCR coating (18) having a second catalytic activity (19), the second catalytic activity (19) being different from the first catalytic activity (16);
arranging a particle filter layer (13) on channel walls (8) of the flow channels (5) that are open at the first end face (6), the particle filter layer (13) having a porosity of from 5 to 50% and an average pore size of from 5 to 15 μm.
13. The process as claimed in claim 12 , wherein at least fee channel walls (8) and the particle filter layer (13) are produced by a printing process.
14. The process as claimed in claim 12 , wherein the particle filter layer (13) is applied by a coating process.
15. The process as claimed in claim 12 , wherein the second catalytic activity (19) is greater than the first catalytic activity (16).
16. The process as claimed in claim 12 , wherein the first SCR coating (15) has a first viscosity (20) and fee second SCR coating (18) has a second viscosity (21), wherein the first viscosity (20) is less than the second viscosity (21).
17. A motor vehicle (3) comprising:
an internal combustion engine (4); and
an exhaust gas system (2), the exhaust gas system (2) having a particle filter (1) as claimed in claim 10 .
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102014112862.1A DE102014112862A1 (en) | 2014-09-08 | 2014-09-08 | Particulate filter and method for producing a particulate filter |
DE102014112862.1 | 2014-09-08 | ||
PCT/EP2015/070387 WO2016037981A1 (en) | 2014-09-08 | 2015-09-07 | Particle filter and method for producing a particle filter |
Publications (1)
Publication Number | Publication Date |
---|---|
US20170284248A1 true US20170284248A1 (en) | 2017-10-05 |
Family
ID=54065880
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/509,399 Abandoned US20170284248A1 (en) | 2014-09-08 | 2015-09-07 | Particle filter and method for producing a particle filter |
Country Status (7)
Country | Link |
---|---|
US (1) | US20170284248A1 (en) |
EP (1) | EP3191696A1 (en) |
KR (1) | KR20170053698A (en) |
CN (1) | CN106795794A (en) |
DE (1) | DE102014112862A1 (en) |
RU (1) | RU2017111878A (en) |
WO (1) | WO2016037981A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114961929A (en) * | 2021-05-14 | 2022-08-30 | 无锡威孚力达催化净化器有限责任公司 | Control method of two-stage post-processing system, device terminal and readable storage medium |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2992172C (en) | 2015-08-14 | 2018-08-28 | Orion Engineered Carbons Gmbh | Methods and systems for particulate matter removal from a process exhaust gas stream |
DE102018104140A1 (en) * | 2018-02-23 | 2019-08-29 | Volkswagen Aktiengesellschaft | Particle filter for an internal combustion engine and method for producing such a particle filter |
DE102018114287A1 (en) * | 2018-06-14 | 2019-12-19 | Dr. Ing. H.C. F. Porsche Aktiengesellschaft | Method for producing at least one ash former for a particle filter of an exhaust system of a gasoline engine |
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DE102004034269A1 (en) * | 2004-07-15 | 2006-02-09 | Volkswagen Ag | Producing a channeled substrate for a catalytic converter or particulate filter for a motor vehicle engine comprises building up the substrate by screen printing |
US20120285148A1 (en) * | 2011-05-13 | 2012-11-15 | Kabushiki Kaisha Toyota Jidoshokki | Catalyst device |
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US20080236145A1 (en) * | 2007-04-02 | 2008-10-02 | Geo2 Technologies, Inc. | Emission Control System using a Multi-Function Catalyzing Filter |
JP4638892B2 (en) * | 2007-03-30 | 2011-02-23 | トヨタ自動車株式会社 | Exhaust gas purification device for internal combustion engine |
DE102008008785A1 (en) * | 2008-02-12 | 2009-08-13 | Man Nutzfahrzeuge Aktiengesellschaft | Device for reducing dibenzo-dioxin, dibenzo-furan and particulate emissions |
DE102008048518A1 (en) * | 2008-09-23 | 2010-03-25 | Man Nutzfahrzeuge Ag | Device for cleaning an exhaust gas stream of an internal combustion engine of a motor vehicle, in particular of a commercial vehicle |
JP5726414B2 (en) * | 2009-11-18 | 2015-06-03 | 日本碍子株式会社 | Catalyst-carrying filter and exhaust gas purification system |
PL2558691T3 (en) * | 2010-04-14 | 2017-01-31 | Umicore Ag & Co. Kg | Diesel particulate filter coated with reduction catalyst with improved characteristics |
WO2011140248A2 (en) * | 2010-05-05 | 2011-11-10 | Basf Corporation | Catalyzed soot filter and emissions treatment systems and methods |
-
2014
- 2014-09-08 DE DE102014112862.1A patent/DE102014112862A1/en not_active Withdrawn
-
2015
- 2015-09-07 EP EP15760439.8A patent/EP3191696A1/en not_active Withdrawn
- 2015-09-07 RU RU2017111878A patent/RU2017111878A/en not_active Application Discontinuation
- 2015-09-07 CN CN201580047927.3A patent/CN106795794A/en active Pending
- 2015-09-07 WO PCT/EP2015/070387 patent/WO2016037981A1/en active Application Filing
- 2015-09-07 US US15/509,399 patent/US20170284248A1/en not_active Abandoned
- 2015-09-07 KR KR1020177009615A patent/KR20170053698A/en not_active Application Discontinuation
Patent Citations (2)
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DE102004034269A1 (en) * | 2004-07-15 | 2006-02-09 | Volkswagen Ag | Producing a channeled substrate for a catalytic converter or particulate filter for a motor vehicle engine comprises building up the substrate by screen printing |
US20120285148A1 (en) * | 2011-05-13 | 2012-11-15 | Kabushiki Kaisha Toyota Jidoshokki | Catalyst device |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114961929A (en) * | 2021-05-14 | 2022-08-30 | 无锡威孚力达催化净化器有限责任公司 | Control method of two-stage post-processing system, device terminal and readable storage medium |
Also Published As
Publication number | Publication date |
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CN106795794A (en) | 2017-05-31 |
KR20170053698A (en) | 2017-05-16 |
WO2016037981A1 (en) | 2016-03-17 |
DE102014112862A1 (en) | 2016-03-10 |
EP3191696A1 (en) | 2017-07-19 |
RU2017111878A (en) | 2018-10-10 |
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