catalyzed soot filter, process for manufacturing a catalyzed soot filter, system for treating a dies

专利摘要:
"Catalyzed soot filter, process for manufacturing a catalyzed soot filter, system for treating a diesel engine exhaust stream, and method for treating a diesel engine exhaust stream". The present invention relates to a catalyzed soot filter comprising a wall-to-wall flow substrate with an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by inner walls of the wall-to-wall flow substrate wherein the plurality of passages comprises inlet passages having an open inlet end and a closed outlet end, and an outlet passage having a closed inlet end and a open outlet end, and the inner walls of the inlet passages comprising a first zoned inlet liner, the inner walls of the outlet passages comprising a first zoned outlet liner, and the first inlet liner and the first coating are present on the wall-to-wall substrate in a coating loading ratio of less than 0.5.
公开号:BR112012012031B1
申请号:R112012012031
申请日:2010-11-22
公开日:2019-12-03
发明作者:Grubert Gerd
申请人:Basf Se；
IPC主号:

专利说明:

CATALYST SOOT FILTER, PROCESS TO MANUFACTURE A CATALYST SOOT FILTER, SYSTEM TO TREAT A DIESEL ENGINE EXHAUST CHAIN, AND METHOD TO TREAT A DIESEL ENGINE EXHAUST CHAIN.
Technical Field [001] The present invention relates to a zonated catalyzed soot filter. This soot filter comprises a wall flow substrate comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by walls internal flow substrate through the wall. The plurality of said passages comprises inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end. The inner walls of the inlet passages comprise a first inlet liner that extends from the inlet end to an end of the first inlet liner, thereby defining a length of the first inlet liner, the length of the first inlet liner being x% of the axial length of the substrate with 0 <x <100. The inner walls of the outlet passages comprise a first outlet liner that extends from the outlet end to an end of the first outlet liner, thereby defining a length of the first outlet liner, the length of the first outlet liner being 100-x% of the axial length of the substrate. The length of the first inlet liner thus defines an upstream zone, and the length of the first outlet liner defines a downstream zone. According to a preferred embodiment, both the first inlet coating and the first outlet coating comprise an oxidation catalyst. According to the present invention, the first inlet liner and the first outlet liner are present on the flow substrate through the wall in a specific liner loading ratio defined as the inlet liner loading relative to the liner loading. output. In particular, said coating load ratio is less than 0.5.
Fundamentals [002] Operation of poorly burning engines such as diesel engines provides the user with excellent fuel economy and has very low emissions of hydrocarbons in the gaseous phase and carbon monoxide due to their operation in high air / fuel ratios under poor conditions. fuel. Diesel engines also offer significant advantages over gasoline engines in terms of their fuel economy, durability, and their ability to generate high torque at low speed. However, there are certain materials contained in diesel engine exhaust gas that are known to cause pollution and therefore can have a serious influence on the environment. In addition to gaseous emissions such as carbon monoxide (“CO”), unburned hydrocarbon (“HC)” and nitrogen oxides (“NOx”), the diesel engine exhaust also contains condensed phase materials, ie liquids and solids , which constitute the so-called particulate matter (“PM”). The total particulate matter emissions contained in diesel engine exhaust comprise, in addition to the soluble organic fraction (soluble organic fraction, “SOF”) and the so-called sulfate fraction, the dry and solid carbonaceous fraction which is also known as the “ soot". This soot contributes to the visible soot emissions commonly associated with diesel exhaust. The soluble organic fraction can exist in diesel exhaust either as a vapor or as an aerosol, i.e. fine droplets of liquid condensate, depending on the temperature of the diesel exhaust. It is usually present as a condensed liquid at the standard particulate collection temperature of 52 ° C in diluted exhaust, as prescribed by a standard measurement test such as the U.S. Heavy Duty Transient Federal Test Procedure ”. These liquids are believed to come from two sources: one, on the one hand, from the lubricating oil removed from the engine cylinder walls each time the pistons rise and fall, and the other, on the other hand, from unburned diesel fuel or only partially burned. It is believed that the sulfate fraction is formed from small amounts of sulfur components present in diesel fuel.
[003] Catalyzed filters are typically applied in diesel engine exhaust systems to achieve high reduction of particulate matter, in particular soot reduction, and to convert certain or all components of the exhaust into harmless components. Known filter structures that remove particulate matter from diesel exhaust include flow filters through honeycomb walls, bundled or rolled fiber filters, open cell foams, sintered metal filters, etc. However, flow filters through the ceramic wall, described below, receive the most attention. Typical ceramic wall flow filter substrates are composed of refractory materials such as cordierite or silicon carbide. Substrates flowing through the wall are particularly useful for filtering particulate matter from exhaust gases from a diesel engine. A common construction is a multi-pass honeycomb structure having the ends of alternating passages capped on the inlet and outlet sides of the honeycomb structure. This construction results in a checkerboard pattern at each end. Covered passages at the axial inlet end are open at the axial outlet end. This allows the exhaust gas with the entrained particulate matter to enter the open inlet passages, flow through the porous inner walls and exit through channels having open outlet axial ends. The particulate matter is thus filtered on the inner walls of the substrate. The pressure of the gas forces the exhaust gas through the porous structural walls into closed channels at the upstream axial end and open at the downstream axial end. The accumulating particles will increase the back pressure of the filter in the engine. Thus, the accumulating particles must be continuously or periodically flared from the filter to maintain an acceptable back pressure. Catalyst compositions deposited along the internal walls of the flow substrate through the wall help in the regeneration of the filter substrates by stimulating the combustion of accumulated particulate matter. The combustion of the accumulated particulate matter restores acceptable backpressures within the exhaust system. These processes can be either regenerative or passive or active processes. Both processes use an oxidizer such as O2 or NO2 to oxidize particulate matter. Passive regeneration processes combustion of particulate matter at temperatures within the normal operating range of the diesel exhaust system. Preferably, the oxidant used in the regeneration process is NO2 because the soot fraction combuses at temperatures much lower than those required when O2 serves as the oxidant. Although O2 is readily available in the atmosphere, NO2 can be actively regenerated through the use of upstream oxidation catalysts that oxidize NO in the exhaust stream.
[004] Despite the presence of catalyst compositions and supplies to use NO2 as the oxidizer, active regeneration processes are generally required to eliminate accumulated particulate matter, and to restore acceptable backpressures within the filter. The soot fraction of the particulate matter generally requires temperatures above 500 ° C to burn under conditions rich in oxygen, i.e. conditions poor in fuel, which are higher temperatures than those typically present in diesel exhaust. Active regeneration processes are usually initiated by changing the engine control to raise temperatures in front of the filter up to 570-630 ° C. Depending on the driving mode, high exotherms can occur inside the filter when cooling during regeneration is not sufficient, such as at low speed / low load or in idle driving mode. Such exotherms can exceed 800 ° C or more inside the filter. In flow filters through a coated wall, exposure to such high temperatures during regeneration events shortens the service life of the coated catalyst compositions along the length of the substrate. In addition, different segments along the axial length of the substrate are disproportionately affected by the regeneration process. Deposition of particulate matter is not homogeneous along the length of the flow filter through the wall, with higher proportions of particulate matter accumulating in the segment downstream of the filter. Consequently, the temperatures are not evenly distributed over the length of the substrate but show a maximum temperature in the downstream segment during active regeneration events. Thus, the durability of the catalyst composition along the downstream segment limits the service life of the flow substrate through the wall coated with the entire catalyst.
[005] High material costs associated with certain oxidation catalysts such as, for example, metal-containing compositions of the platinum group increase the need to slow down or avoid degradation of catalyst coatings due to active regeneration events. Catalyst coatings positioned on wall flow filters often contain platinum group metal components as active catalyst components to ensure acceptable conversions of gaseous emissions such as HC and / or CO from diesel exhaust into harmless components (eg, CO2, H2O). The loads of such components are generally adjusted so that the catalyst substrate meets emission regulations even after the catalyst has aged.
[006] Certain conventional coating designs for flow substrates through the wall have a homogeneous coating distribution along the entire axial length of the inner walls. In such projects the concentration of oxidation catalyst is typically adjusted to meet emissions requirements under the most stringent conditions. Most of the time, these conditions refer to the performance of the catalyst after the aging of the catalyst. The cost associated with the metal concentration of the platinum group is often higher than desired.
[007] Other conventional coating designs for flow substrates through the wall use gradients of concentration of the metal components of the platinum group along the axial length of the substrate.
[008] In these designs certain catalyst zones, e.g., an upstream zone, have a higher concentration of platinum group metals than the adjacent axial zones such as, e.g., a downstream zone. Typically, the inner walls of the axial zone where the highest concentration of platinum group metal components are positioned, will have a lower permeability than that of an adjacent zone having a lower concentration of platinum group metals due to a loading higher washcoat (high catalyst supporting surface area covering layer). An exhaust current passing along the length of the inlet passage will pass through the inner wall in the segments that have the highest permeability. Thus, the gas stream will tend to flow through segments of the inner wall that have a lower concentration of oxidation catalyst. This differential flow pattern can result in inappropriate pollutant conversion. For example, certain gaseous pollutants, e.g., unburned hydrocarbons, require contact with higher concentrations of platinum group metal components than particulate components to achieve sufficient levels of combustion. This requirement is exacerbated during operating conditions in which the exhaust temperatures are cooler, e.g., at startup.
[009] EP 1.870.573 A1 discloses a diesel particulate filter comprising a plurality of cells that are partitioned by porous cell walls and are closed in a staggered manner by plugs at one end upstream of the filter and at one end thereof downstream opposites being that a first layer of oxidation catalyst coating is formed over the entire surface of the cell walls of cells that are open at the upstream end of the filter, and a second layer of oxidation catalyst coating is formed on the surfaces the cell walls of the cells that are open at the downstream end of the filter, at a downstream part of the filter. Thus, this document reveals filters having a region of cell walls dividing the cells that are open at the upstream end and the cells that are open at the downstream end with the catalyst coating layers of the respective cells overlapping, due to the fact that the first oxidation catalyst coating layer is formed over the entire surface of the respective cell walls.
[0010] WO 01/12320 A1 discloses a flow filter through the wall for a combustion engine exhaust system, whose filter comprises a plurality of channels in honeycomb arrangement, at least some of the channels are covered at one end upstream and at least some of the channels not capped at the end upstream are capped at one end downstream; an oxidation catalyst in a substantially gas-impermeable zone at an upstream end of the capped channels at the downstream end; and a gas-permeable filter zone downstream of the oxidation catalyst to retain soot, characterized by the fact that in an exhaust system the oxidation catalyst is capable of generating enough NO2 from NO to continuously combust the soot trapped in a temperature below 400 ° C. According to this document, coatings on opposite sides of a given cell wall are applied in such a way that there is a region of the cell wall that is free of coating on both sides in order to allow a permeable zone to gas. [0011] EP 1,486,248 A1 discloses an integrated multifunctional catalyst system comprising a diesel particulate filter having an inlet side to receive flow and an opposite outlet side; a substrate in the diesel particulate filter having an inner wall surface and an outer wall surface; a first washcoat layer applied to the inner wall surface and adjacent to the inner side; and a second washcoat layer applied to the outer wall surface and adjacent to the outlet side, with flow distribution through the substrate dispersed to minimize back pressure. According to a preferred embodiment, the first washcoat layer occupies a first substrate length, the second washcoat layer occupies a second substrate length, the sum of the first length and the second length being approximately equal to a total length of the substrate. substrate. According to an even more preferred embodiment, EP 1,486,248 A1 discloses a diesel particulate filter having an inlet side for receiving flow and an opposite outlet side; a plurality of honeycomb cells within the diesel particulate filter, with alternating outlet rods being blocked on the inlet side and alternating inlet channels are blocked on the opposite outlet side; a substrate for each of the input channels, each substrate having an inner wall surface and an outer wall surface; a first washcoat layer applied to the inner wall surface and the adjacent inlet side; and a second washcoat layer, applied to the outer wall surface and the adjacent outlet side, the flow distribution through the substrate being dispersed to minimize back pressure, it is stated that this second washcoat layer contains a different function than the first washcoat layer.
[0012] WO 2006/031600 A1 discloses a zonated catalyzed soot filter having a flow substrate through the wall with an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the end of exit, and a plurality of passages defined by internal walls of the flow substrate through the wall. The plurality of passages has inlet passages with an open inlet end and a closed outlet end, and outlets with a closed inlet end and an open outlet end. The inner walls of the inlet passages have a first inlet liner that extends from the inlet end to an end of the first inlet liner, thereby defining a length of the first inlet liner. The length of the first inlet liner is less than the axial length of the substrate. The inner walls of the outlet passageways have an outlet liner that extends from the outlet end to an outlet liner end, thereby defining an outlet liner length. The output coating length is less than the axial length of the substrate. The sum of the length of the first inlet liner and the length of the outlet liner is substantially equal to the axial length of the substrate. The length of the first inlet liner defines an upstream zone and the length of the outgoing liner defines a downstream zone. The first entry liner contains at least one metal component of the first entry stage group. At least 50% of the metal components of the platinum group are present in the upstream zone. According to the teaching of this document, the washcoat loading ratio, defined as the washcoat loading of the first inlet zone relative to the washcoat loading of the outlet liner, is within the range of 0.5 to 1.5. Thus, this document does not differentiate between modalities in which the washcoat loading proportion is greater than or less than 1. In addition, a specific lower limit for the washcoat loading proportion is defined, namely a limit of 0.5 .
[0013] Generally, when an active regeneration of a catalyzed soot filter used in a diesel exhaust system is interrupted during its operation, eg when the engine is idling, very high temperatures occur at the rear end of the catalyzed soot filter. by the uncontrolled burning of soot. The maximum temperature at the rear of the filter is believed to decrease with soot loading at the rear of the filter. The maximum soot load on the filter, often called the soot mass limit, “SML” is determined by its maximum temperature. An objective of the present invention was to obtain a catalyzed soot filter that allows an increased soot mass loading (“SML”) and therefore a maximum decreased temperature.
[0014] Therefore, the present invention is directed to a catalyzed soot filter that has a coating design that allows a maximum temperature during regeneration during a fall to idle and a high soot mass limit.
Summary s [0015] A catalyzed soot filter is obtained, comprising: a wall-flow substrate comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end , and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; the inner walls of the inlet passages comprising a first inlet liner extending from the inlet end to an end of the first inlet liner, thereby defining a length of the first inlet liner, the length of the first liner of input is x% of the axial length of the substrate with 0 <x <100; the inner walls of the outlet passages comprising a first outlet liner extending from the outlet end to an end of the first outlet liner, thereby defining a length of the first outlet liner, the length of the first liner being output is 100-x% of the axial length of the substrate; the length of the first inlet liner defining an upstream zone and the length of the first outlet liner defining a downstream zone; the first inlet coating and the first outlet coating are present on the flow substrate through the wall in a coating load ratio of less than 0.5, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: loading the second inlet liner [g / inch3 (g / (2.54 cm) 3)].
[0016] Preferably, a catalyzed soot filter is obtained, comprising: a substrate flowing through the wall comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end , and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; the inner walls of the inlet passages comprising a first inlet liner extending from the inlet end to the end of the first inlet liner, thereby defining a length of the first inlet liner, the length of the first liner of inlet is x% of the axial length of the substrate with 0 <x <100, said first inlet coating containing an oxidation catalyst; the inner walls of the outlet passages comprising a first outlet liner extending from the outlet end to an end of the first outlet liner, thereby defining a length of the first outlet liner, the length of the first liner being output is 100-x% of the axial length of the substrate, said first output coating containing an oxidation catalyst; the length of the first inlet liner defining an upstream zone and the length of the first outlet liner defining a downstream zone; the first inlet coating and the first outlet coating are present on the flow substrate through the wall in a coating load ratio of less than 0.5, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: loading the second inlet liner [g / inch3 (g / (2.54 cm) 3)].
[0017] Furthermore, a process is provided to manufacture such a catalyzed soot filter, comprising: (i) obtaining a flow substrate through the wall, preferably having a porosity within the range of 38 to 75, determined according to porosity measurement with mercury according to DIN 66133, said flow substrate through wall comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; (ii) applying the first inlet liner to the inner walls of the inlet passages such that the first inlet liner extends from the inlet end to the end of the first inlet liner by means of which a length of the first liner is defined input, the length of the first input coating being x% of the axial length of the substrate with 0 <x <100, thereby adjusting the loading of the first input coating to a predetermined value that is preferably within the range of [0 , 1 to 1 g / inch3 (g / (2.54 cm) 3]; (iii) before (ii) or simultaneously with (ii) or after (ii), apply the first exit coating on the inner walls of the passages outlet so that the first outlet liner extends from the outlet end to the end of the first outlet liner by means of which a length of the first outlet liner is defined, the length of the first outlet liner is 100-x% of the axial length of the substrate, thereby adjusting the loading of the first outlet liner to a value such that the proportion of liner loading, calculated as the proportion of the loading of the first liner [g / inch3 (g / (2.54 cm) 3)]: loading the first output liner [g / inch3 (g / (2.54 cm) 3)] is less than 0.5, preferably within from 0.10 to 0.45, more preferably from 0.20 to 0.40, more preferably from 0.30 to 0.35.
[0018] Preferably, additionally, a process is provided to manufacture such a catalyzed soot filter, comprising: (i) obtaining a flow substrate through the wall, preferably having a porosity within the range of 38 to 75, determined according to measurement of mercury porosity according to DIN 66133, said flow substrate through wall comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; (ii) applying the first inlet liner to the inner walls of the inlet passages such that the first inlet liner extends from the inlet end to the end of the first inlet liner by means of which a length of the first liner is defined input, the length of the first input coating being x% of the axial length of the substrate with 0 <x <100, said first input coating containing an oxidation catalyst, thus adjusting the loading of the first input coating to a predetermined value that is preferably within the range of [0.1 to 1 g / inch3 (g / (2.54 cm) 3)]; (iii) before (ii) or simultaneously with (ii) or after (ii), apply the first outlet liner to the inner walls of the outlet passages in such a way that the first outlet liner extends from the outlet end to the end of first outlet coating through which a length of the first outlet coating is defined, the length of the first outlet coating being 100-x% of the axial length of the substrate, said first outlet coating containing an oxidation catalyst , thereby adjusting the loading of the first outlet liner to a value such that the proportion of liner loading, calculated as the proportion of the loading of the first liner [g / inch3 (g / (2.54 cm) 3)] : loading of the first outlet liner [g / inch3 (g / (2.54 cm) 3)] is less than 0.5, preferably within the range of 0.10 to 0.45, more preferably 0, 20 to 0.40, m preferably from 0.30 to 0.35. [0019] A system is also provided to treat a diesel engine exhaust gas stream, the system comprising an exhaust duct in fluid communication with the diesel engine via an exhaust manifold; such a catalyzed soot filter; and one or more of the following in fluid communication with the catalyzed soot filter: a diesel oxidation catalyst article (DOC); a selective catalytic reduction (SCR) article; a NOx storage and reduction catalytic article (NOx storage and reduction, NSR).
[0020] Furthermore, a method of treating a diesel engine exhaust stream, the exhaust stream containing soot particles, is provided, said method comprising contacting the exhaust stream with such a catalyzed soot filter, optionally after directing the stream exhaust through a diesel oxidation catalyst (DOC) article, said DOC article preferably comprising a flow through substrate or a flow substrate through wall.
[0021] Furthermore, the use of such a catalyzed soot filter is provided for the treatment of a diesel engine exhaust stream, optionally in combination with a diesel oxidation catalyst (DOC) article and / or a selective catalytic reduction article ( SCR) and / or a NOx reduction and storage catalyst (NSR) article.
Brief Description of the Drawings [0022] Fig. 1 a sketch of the zonated catalytic soot filter (CSF) with a higher washcoat load in the CSF exit zone with an inlet length extended by 50% and an outlet coating in length extended by 50%. In Fig. 1, 1 shows the entry liner. 2 shows the outlet liner having a higher washcoat load than the inlet liner. 3 shows the filter substrate plug to close the inlet channel. 4 shows the filter substrate plug to close the outlet channel.
[0023] The arrow indicates the direction of flow through the CSF.
[0024] Fig. 2 shows a sketch of the zonated catalyzed soot filter with a higher washcoat load in the CSF exit zone with a washcoat gradient over the axial substrate length. In Fig. 2, 1 shows the entry liner. 2 shows the outlet liner having a higher washcoat loading than the inlet liner, 3 shows the second outlet liner on top of the outlet liner 2. 4 shows the filter substrate plug to close the inlet channel, 5 shows the plug of the filter substrate to close the outlet channel.
[0025] The arrow indicates the direction of flow through the CSF.
[0026] Fig. 3 shows the positioning of thermocouples 1 to 4 in samples A and B for regeneration during a fall to idle according to the Example. Thermocouple 1 is located 2.54 cm from the CSF inlet end, thermocouple 2 is located 7.62 cm from the CSF inlet end, thermocouple 3 is located 10.16 cm from the CSF inlet end, and thermocouple 4 is located 10.16 centimeters from the input end of the CSF.
[0027] The arrow indicates the direction of flow through the CSF.
[0028] Fig. 4 shows temperature versus time curve during the drop to idle test for the 4 thermocouples for sample A according to the example of the invention. In Fig. 4, thermocouple 1 is identified as 1 ”, thermocouple 2 is identified as 2”, thermocouple 3 is identified as 3 ”, and thermocouple 4 is identified as 4”.
[0029] Fig. 5 shows temperature versus time curve during the drop to idle test for the 4 thermocouples for sample B according to the comparative example. In Fig. 5, thermocouple 1 is identified as 1 ”, thermocouple 2 is identified as 2”, thermocouple 3 is identified as 3 ”, and thermocouple 4 is identified as 4”.
Detailed Description [0030] The present invention relates to a catalyzed soot filter, comprising a wall-flow substrate comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; the inner walls of the inlet passages comprising a first inlet liner extending from the inlet end to an end of the first inlet liner, thereby defining a length of the first inlet liner, the length of the first liner of input is x% of the axial length of the substrate with 0 <x <100; the inner walls of the outlet passages comprising a first outlet liner extending from the outlet end to an end of the first outlet liner, thereby defining a length of the first outlet liner, the length of the first liner being output is 100-x% of the axial length of the substrate; the length of the first inlet liner defining an upstream zone and the length of the first outlet liner defining a downstream zone; the first inlet coating and the first outlet coating are present on the flow substrate through the wall in a coating load ratio of less than 0.5, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: loading the first outlet liner [g / inch3 (g / (2.54 cm) 3)].
[0031] According to a preferred embodiment of the present invention, said first inlet coating contains an oxidation catalyst. According to another preferred embodiment of the present invention, said first outlet coating contains an oxidation catalyst. More preferably, both the first inlet coating and the first outlet coating comprise an oxidation catalyst.
[0032] According to the present invention, the washcoat loading ratio calculated as the loading ratio of the first inlet liner: loading of the first outlet liner is less than 0.5. Surprisingly, it was found that by applying said first inlet liner and said first outlet liner such that the washcoat loading ratio is less than 0.5, the SML could be increased and the maximum temperature required for regeneration during a fall to idle it could be decreased. In addition, it was found that such washcoat loading proportions of less than 0.5 allowed a lower frequency of active regeneration of the catalyzed soot filter while driving the vehicle.
[0033] According to preferred embodiments of the present invention, the washcoat loading ratio calculated as the loading ratio of the first inlet liner: loading of the first outlet liner is less than 0.49, more preferably less than 0.45 . More preferably, said washcoat coating ratio is within the range of 0.05 to 0.49, more preferably within the range of 0.1 to 0.45. Even more preferred embodiments are directed to said washcoat coating ratio which is within the range of 0.15 to 0.45, more preferably within the range of 0.15 to 0.40, more preferably within the range of 0.20 to 0.40. Especially preferred are washcoat coating proportions that are within the range of 0.25 to 0.40, more preferably from 0.25 to 0.35, more preferably from 0.30 to 0.35 such as, for example, 0 , 30, 0.31, 0.32, 0.33, 0.34, 0.35.
[0034] The term "washcoat coating" of a given coating as used in the context of the present invention refers to a loading which is determined by measuring the weight of the flow substrate through the wall used in accordance with the present invention before and after the respective washcoat loading has been applied, followed by drying and calcination of the catalyzed soot filter as described here below.
[0035] According to preferred embodiments of the present invention, the loading of the inlet liner is within the range of 0.1 to 1 g / inch3 (g / (2.54 cm) 3)]. Even more preferably, said loading is within the range of 0.1 to 0.5 g / inch3 (g / (2.54 cm) 3)].
[0036] According to the present invention, the length of the first inlet liner is x% of the axial length of the substrate with 0 <x <100, and the length of the first outlet liner is 100-x% of the axial length of the substrate . Consequently, the sum of the length of the first inlet liner and the length of the first outlet liner can be equal to the axial length of the substrate. However, it is to be understood that, due to manufacturing techniques, the length of the first inlet coating and the length of the first outlet coating can overlap a certain portion ("overlapping region"). It is also conceivable that the sum of the length of the first inlet liner and the length of the first outlet liner is slightly less than the axial length of the substrate resulting in a small gap between the end of the first liner and the end of first exit coating being that in a given internal wall, a given portion of said internal wall is not coated with the first entrance coating nor coated with the first exit coating ("gap region"). Generally, such regions of gap region and / or overlap regions of the given inner wall, if present, are at most 1% of the axial length of the substrate, preferably at most 0.5% of the axial length of the substrate, more preferably at most 0.1% of the axial length of the substrate. Even more preferably, the catalyzed soot filter of the present invention does not have such gap regions.
[0037] As defined above, the length of the first inlet coating is x% of the axial length of the substrate with 0 <x <100, and the length of the first outlet coating is 100-x% of the axial length of the substrate. Typically, x is within the range of 1 to 99, preferably from 5 to 95, more preferably from 10 to 90, more preferably from 15 to 85, more preferably from 20 to 80. According to a preferred embodiment of the present invention in which the catalyzed soot filter contains only one inlet coating and only one outlet coating, ie in which the catalytic soot filter coatings consist of the first inlet coating and the first outlet coating, x is preferably within the range of 25 to 75, more preferably from 30 to 70, more preferably from 35 to 65, more preferably from 40 to 60, more preferably from 45 to 55. In particular, if the catalyzed soot filter coatings consist of the first inlet coating and the first exit coating, x is within the range of 47 to 53 such as 47, 48, 49, 50, 51, 52, or 53, more preferably 48 to 52, more preferably 49 to 51.
[0038] According to the present invention, the first inlet coating and the first outlet comprise an oxidation catalyst. In this context, the term "oxidation catalyst" as used in the context of the present invention also refers to the embodiment in which in the first inlet coating, at least one oxidation catalyst is contained, and in which in the first inlet coating, at least an oxidation catalyst is contained. The at least one oxidation catalyst contained in the first inlet coating may be the catalyst equal to or different from the at least one oxidation catalyst contained in the first inlet coating.
[0039] Preferably, the oxidation catalyst contained in the first inlet coating is a component of the platinum group metal (platinum group metal, "PGM"). The term "PGM" as used in the context of the present invention refers to ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). Preferred oxidation catalysts contained in the first inlet coating are PGM components with PGM being selected from the group consisting of Pt, Pd, Rh, Ir and a mixture of two or more of them. Most preferably, PGM is selected from the group consisting of Pt, Pd, and a mixture of Pt and Pd. Even more preferably, the PGM consists of a mixture of Pd and Pt.
[0040] If PGM of the first inlet coating contains, preferably consists of a mixture of Pd and Pt, there are no specific restrictions as long as the weight ratio of Pt: Pd is considered. Typically, the weight ratio in the first inlet coating is within the range of 10: 1 to 1:10, preferably from 9: 1 to greater than 1: 1, more preferably from 8: 1 to 1.1: 1, more preferably from 7: 1 to 1.2: 1, more preferably from 6: 1 to 1.3: 1, more preferably from 5: 1 to 1.4: 1, more preferably from 4: 1 to 1.5: 1.
[0041] Typically, the first inlet coating of the catalyzed soot filter of the present invention comprises the oxidation catalyst in an amount of 5 to 100 g / ft3 (g / (30.48 cm) 3), more preferably 7 to 90 g / ft3 (g / (30.48 cm) 3), more preferably 8 to 80 g / ft3 (g / (30.48 cm) 3), more preferably 9 to 70 g / ft3 (g / ( 30.48 cm) 3), more preferably from 10 to 60 g / ft3 (g / (30.48 cm) 3). As for the preferred embodiment in which the oxidation catalyst of the first inlet coating is at least a PGM component, the term "amount of oxidation catalyst" as used in the context of the present invention refers to the weight of the at least one PGM in the final catalyzed soot filter, ie in the catalyzed soot filter after drying and calcination as described here below.
[0042] Preferably, the oxidation catalyst contained in the first outlet coating is a PGM component. Preferred oxidation catalysts contained in the first outlet coating are PGM components with PGM being selected from the group consisting of Pt, Pd, Rh, Ir and a mixture of two or more of them. Most preferably, PGM is selected from the group consisting of Pt, Pd, and a mixture of Pt and Pd. Even more preferably, the PGM consists of a mixture of Pd and Pt.
[0043] If the PGM of the first exit coating contains, preferably consists of a mixture of Pd and Pt, there are no specific restrictions as long as the weight ratio of Pt: Pd is considered. Typically, the weight ratio in the first output coating is within the range of 10: 1 to 1:10, preferably from 9: 1 to greater than 1: 1, more preferably from 8: 1 to 1.1: 1, more preferably from 7: 1 to 1.2: 1, more preferably from 6: 1 to 1.3: 1, more preferably from 5: 1 to 1.4: 1, more preferably from 4: 1 to 1.5: 1.
[0044] Therefore, the present invention also relates to a catalyzed soot filter as described above, the first inlet coating and the first outlet coating comprising an oxidation catalyst consisting of platinum and palladium, the proportion being by weight of platinum: palladium in the first inlet coating is within the range of 10: 1 to 1:10, preferably from 4: 1 to 1.5: 1, and the weight ratio of platinum: palladium in the first coating output is within the range of 10: 1 to 1:10, preferably 4: 1 to 1.5: 1.
[0045] Typically, the first outlet coating of the catalyzed soot filter of the present invention comprises the oxidation catalyst in an amount of 5 to 100 g / ft3 (g / (30.48 cm) 3), more preferably 7 to 90 g / ft3 (g / (30.48 cm) 3), more preferably 8 to 80 g / ft3 (g / (30.48 cm) 3), more preferably 9 to 70 g / ft3 (g / ( 30.48 cm) 3), more preferably from 10 to 60 g / ft3 (g / (30.48 cm) 3). As for the preferred embodiment in which the oxidation catalyst of the first outlet coating is at least a PGM component, the term "amount of oxidation catalyst" as used in the context of the present invention refers to the weight of the at least one PGM in the final catalyzed soot filter, ie in the catalyzed soot filter after drying and calcination as described here below.
[0046] According to a first preferred embodiment of the present invention, the oxidation catalyst content, preferably the PGM content, of the upstream zone is less than the oxidation catalyst content, preferably the PGM content, of the upstream zone downstream. Generally, the proportion of PGM, defined as the total amount of PGM contained in the first inlet coat (g / ft3 (g / (30.48 cm) 3) divided by the total amount of PGM contained in the first outward coat (g / ft3 (g / (30.48 cm) 3) is less than 1, preferably within the 1:10 to 1: 2 range. The PGM ratio is preferably within the 1: 9 to 1: 2 range, more preferably from 1: 8 to 1: 3, and more preferably from 1: 7 to 1: 3.
[0047] Surprisingly, it was found that the washcoat loading of the invention, together with the PGM content of the first inlet coating which is less than the PGM content of the first outlet coating, has advantages for example as a pre-SCR application when a NO2 / NOx ratio of eg 50% is required in emissions from the catalyzed soot filter to the SCR catalyst, in which case only a low PGM charge in the upstream zone is required for gas activity, compared to a more high of PGM in the downstream zone. Thus PGM can be saved in the area upstream of the catalyzed soot filter.
[0048] According to a second preferred embodiment of the present invention, the oxidation catalyst content, preferably the PGM content, of the upstream zone is higher than the oxidation catalyst content, preferably the PGM content, of the downstream zone. Generally, the proportion of PGM, defined as the total amount of PGM contained in the first inlet coat (g / ft3 (g / (30.48 cm) 3) divided by the total amount of PGM contained in the first outward coat (g / ft3 (g / (30.48 cm) 3) is greater than 1, preferably within the range of 2: 1 to 10: 2. The proportion of PGM is preferably within the range of 2: 1 to 9: 1, more preferably 3: 1 to 8: 1, and more preferably 3: 1 to 7: 1.
[0049] Surprisingly, it has been found that the washcoat loading of the invention, together with the PGM content of the first inlet coating which is higher than the PGM content of the first outlet coating results in an HC gas conversion activity / CO higher compared to a soot filter catalyzed with a homogeneous distribution of PGM over the length of the substrate. Thus, it was found that this modality has advantages, for example, as applying only CSF and downstream a DOC, when the catalyzed soot filter needs to have an HC / CO gas conversion activity. In this case the loading of PGM in the upstream zone is mainly contributing to the gas activity. Thus PGM can be saved in the downstream zone of the catalyzed soot filter compared to a catalyzed soot filter with a homogeneous distribution of PGM over the length of CSF.
[0050] According to an especially preferred embodiment of the present invention, the oxidation catalyst content, preferably the PGM content, of the upstream zone is higher than the oxidation catalyst content, preferably the PGM content, of the downstream zone.
[0051] According to a preferred embodiment of the present invention, the first inlet coating comprises at least one porous support material. Although there are no specific restrictions, it is preferred that the porous support material is a refractory metal oxide. More preferably, the porous support material of the first inlet coating is selected from the group consisting of alumina, zirconia, silica, titania, a rare earth metal oxide such as cerium, praseodymium, lanthanum, neodymium and samarium oxide, silica -alumina, alumino-silicates, alumina-zirconia, alumina-chromium, alumina-rare earth metal oxide, titania-silica, titania-zirconia, titania-alumina, and a mixture of two or more of the same.
[0052] More preferably, the at least one porous support material is selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
[0053] According to a preferred embodiment of the present invention, the first outlet coating comprises at least one porous support material. Although there are no specific restrictions, it is preferred that the porous support material is a refractory metal oxide. More preferably, the porous support material of the first outlet coating is selected from the group consisting of alumina, zirconia, silica, titania, a rare earth metal oxide such as cerium, praseodymium, lanthanum, neodymium and samarium oxide, silica -alumina, alumino-silicates, alumina-zirconia, alumina-chromium, alumina-rare earth metal oxide, titania-silica, titania-zirconia, titania-alumina, and a mixture of two or more of the same.
[0054] More preferably, the at least one porous support material is selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
[0055] Therefore, the present invention also relates to a catalyzed soot filter as described above, the first inlet and first outlet liners comprising at least one porous support material, the at least one material being porous support material of the first inlet coating is preferably selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of them, and the at least one porous support material of the first outlet coating is preferably selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of them.
[0056] According to a preferred embodiment, the refractory metal oxide of the first inlet coating and / or the first outlet coating essentially consists of alumina, more preferably gamma-alumina or activated alumina, such as gamma- or etha- alumina. Preferably, the activated alumina has an average surface area, determined according to the measurement of the BET surface area according to DIN 66131, from 60 to 300 m2 / g, preferably from 90 to 200 m2 / g, more preferably from 100 to 180 m2 / g.
[0057] Wall flow substrates useful for the catalyzed soot filter of the present invention have a plurality of thin, substantially parallel flow passages extending along the longitudinal axis of the substrate. Each passage is blocked at one end of the substrate body, with alternating passages blocked at opposite end faces. Such monolithic supports can contain up to about 400 flow passages (or "cells") per square inch (6,452 cm2) in cross section, although much less can be used. For example, the support may have from 7 to 400, preferably from 100 to 400, cells per square inch (cells per square inch, "cpsi") (cells per 6.45 cm2). The cells can have cross sections that are rectangular, square, circular, oval, triangular, hexagonal, or are of other polygonal shapes.
[0058] Preferred wall-flow substrates are composed of ceramic-like materials such as cordierite, alpha-alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate, or refractory metals such as stainless steel. Preferred wall-flow substrates are formed from cordierite and silicon carbide. Such materials are able to withstand the environment, particularly high temperatures, found in the treatment of exhaust currents. Flow substrates through ceramic walls are typically formed of material having a porosity of about 40 to 70. The term “porosity” as used in the context is understood to be determined according to the measurement of porosity with mercury according to DIN 66133 .
[0059] In accordance with the present invention, flow-through substrates having a porosity within the range of 38 to 75, more preferably 55 to 70, are preferred.
[0060] For example in some configurations, a flow substrate through the wall having a porosity of 60 and an average pore diameter of about 15-25 micrometers provides adequate exhaust flow. Other specific modalities are, for example, configurations that use 100 cpsi wall flow substrates that have a 17 mil wall (1 thousand corresponds to 0.0254 mm), and a 300 cpsi wall flow substrate and a wall of 12-14 thousand.
[0061] Generally, there are no restrictions regarding the axial substrate lengths of the catalyzed soot filter of the present invention. Axial substrate lengths will mainly depend on the intended use of the catalyzed soot filter of the present invention. Typical axial lengths of catalytic soot filter substrate used, for example, in the automotive area are within the range of 4 to 10, preferably 6 to 8 inches (1 inch = 2.54 cm).
[0062] Each of the coatings of the present invention on the flow through wall substrate is formed of a respective washcoat composition that contains at least one porous support material as described above. Other additives such as binders and stabilizers can also be included in the washcoat composition. Such stabilizers can be included either in the first inlet coat or in the first outlet coat or in other outlet coatings, as described here below. As disclosed in United States Patent No. 4,727,052, porous support materials, such as activated alumina, can be thermally stabilized with respect to the transformations of the alumina phase from gamma to alpha at elevated temperatures. Stabilizers can be selected from at least one of the alkaline earth metal components selected from the group consisting of magnesium, barium, calcium and strontium, preferably strontium and barium. When present, stabilizing materials are added at about 0.01 g / in3 (g / (2.54 cm) 3) to 0.15 g / in3 (g / (2.54 cm) 3) in the coating.
[0063] A certain coating is positioned on the surface of the inner walls. In addition, it is conceivable that a particular coating is positioned over another coating that had been applied on the surface of the internal walls or on yet another coating. Modalities of the present invention with two or more coatings, in particular two or more outlet coatings, are described here below. In addition, a given coating may partially permeate the porous internal walls or the coating on which it is applied.
[0064] A certain washcoat can be applied as a coating according to any conceivable method. For example, it is conceivable to apply a washcoat by spraying a washcoat on the internal walls of the flow substrate through the wall. In accordance with the present invention, it is preferred to apply a particular washcoat to the internal walls of the flow substrate through a dip-coated wall.
[0065] In particular if PGM components are used as oxidation catalysts, a washcoat composition to be applied to the inner walls of the flow substrate through the wall is preferably prepared by dispersing a suitable PGM component precursor over a support material. suitable porous material, preferably a suitable refractory metal oxide as described above. More preferably, a water soluble or water dispersible PGM component precursor is impregnated on a suitable porous support material, preferably a suitable refractory metal oxide, followed by drying and fixing steps. Suitable PGM component precursors include, for example, platinum potassium chloride, platinum ammonium thiocyanate, platinum hydroxide solubilized with amine, chloro-platinum acid, palladium nitrate, rhodium chloride, rhodium nitrate, rhodamine hexamine chloride, and similar. Other suitable PGM component precursors will be apparent to those skilled in the art. The impregnated support material is preferably dried with the PGM component fixed thereon. Generally, drying temperatures are within the range of 60 ° C to 250 ° C, preferably 90 ° C to 210 ° C, more preferably 100 ° C to 150 ° C. Drying can be carried out in any suitable atmosphere, with nitrogen or air. After drying, it is finally preferred to fix the PGM component on the support material by suitable calcination and / or other suitable methods such as treatment with acetic acid. In general, any method that results in the water-insoluble form of the PGM component is suitable. Generally, calcination temperatures are within the range of 250 ° C to 800 ° C, preferably 350 ° C to 700 ° C, more preferably 400 ° C to 600 ° C. Calcination can be carried out in any suitable atmosphere, with nitrogen or air. For example, by calcination, the elementally PGM s catalytically active or its oxide is obtained. It is to be understood that the term "PGM component" present in the final catalyzed soot filter as used in the context of the present invention refers to PGM in the form of the catalytically active elementary PGM, or its oxide, or the mixture of elementary and PGM your oxide.
[0066] Thus, the present invention also relates to a process for making a catalyzed soot filter as described above, the process comprising: (i) obtaining a flow substrate through the wall, preferably having a porosity within the range of 38 at 75, determined according to porosity measurement with mercury according to DIN 66133, said flow substrate through wall comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; (ii) applying the first inlet liner to the inner walls of the inlet passages such that the first inlet liner extends from the inlet end to the end of the first inlet liner by means of which a length of the first liner is defined input, the length of the first input coating being x% of the axial length of the substrate with 0 <x <100, thereby adjusting the loading of the first input coating to a predetermined value that is preferably within the range of 0, 1 to 1 g / inch3 (g / (2.54 cm) 3); (iii) before (ii) or simultaneously with (ii) or after (ii), apply the first outlet liner to the inner walls of the outlet passages in such a way that the first outlet liner extends from the outlet end to the end of the first outlet liner through which a length of the first outlet liner is defined, the length of the first outlet liner being 100-x% of the axial length of the substrate, thereby adjusting the loading of the first outlet liner to a value such that the coating loading ratio, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: loading the first outlet coating [g / inch3 (g / (2.54 cm) 3)] is less than 0.5, preferably within the range of 0.10 to 0.45, more preferably from 0.20 to 0.40, more preferably from 0, 30 to 0.35.
[0067] According to a preferred embodiment of the present invention, said first inlet coating contains an oxidation catalyst. According to another preferred embodiment of the present invention, said first outlet coating contains an oxidation catalyst. More preferably, both the first inlet coating and the first outlet coating comprise an oxidation catalyst.
[0068] According to an embodiment of the present invention, the catalyzed soot filter contains a first inlet coating, a first outlet coating, and additionally comprises at least one other outlet coating. Generally, the catalyzed soot filter of the present invention can additionally contain k other outlet coatings, with k being an integer with k> 1. Preferably, the catalyzed soot filter of the present invention can contain up to 9, more preferably up to 7, more preferably up to 5, and more preferably up to 3 additional outlet coatings, such as 1, 2, or 3 additional outlet coatings. [0069] Much more preferably, the (j + 1) -th eighth outlet of the catalyzed soot filter of the present invention is located on top of the j-th egress outlet. For example, if the catalyzed soot filter contains 3 additional outlet liners, the second outlet liner, ie the first additional outlet liner (where j = 1) is located on top of the first outlet liner, the third outlet liner, ie the second additional outlet liner (where j = 2) is located on top of the second outlet liner, and the fourth outlet, ie the third additional outlet liner (where j = 3) is located on top of the third outlet liner.
[0070] Typically, a given additional outlet liner extends from the (total) outlet end of the catalyzed soot filter to the respective end of this outlet liner. Thus, the length of this outlet liner is defined. Generally speaking, the (j + 1) -th eighth outlet of the catalyzed soot filter of the present invention extends from the outlet end to a (j + 1) -th eighth end of the outlet lining, thereby defining one (j + 1) -th exit coating length.
[0071] Generally, it is conceivable that the length of the outlet liner of a given outlet liner is less than or equal to the length of the outlet liner of the outlet liner on which said particular liner is located. For example, if the catalyzed soot filter contains 3 additional outlet liners, the second outlet liner, ie the first additional outlet liner (in which j = 1) is located on top of the first outlet liner where the length of the second outlet liner is less than or equal to the length of the first outlet liner, the third outlet liner, ie the additional second outlet liner (where j = 2) is located on top of the second liner outlet being that the length of the third outlet liner is less than or equal to the length of the second outlet liner, and the fourth outlet, ie the additional third outlet liner (where j = 3) is located on top of the third outlet liner, the length of the fourth outlet liner being less than or equal to the length of the third outlet liner. Generally speaking, the length of the (j + 1) -th egress lining is yj + 1% of the length of the j-th egress lining length with 0 <yj + 1 <100.
Therefore, the present invention also relates to a catalyzed soot filter as previously described, the catalyzed soot filter additionally comprising k other outlet coatings, the (j + 1) -th outlet coat being located on the top of the j-th exit liner, said (j + 1) -th exit lining extending from the exit end to the (j + 1) -th exit lining end, thereby defining the length of (j +1) -th exit coat, with the length of (j + 1) -th exit coat is yj + 1% of the length of the j-th exit coat with 0 <yj + i <100; with k being an integer with k> 1, k preferably being within the range 1 to 4, more preferably 1 to 3; and where j is an integer with 1 <j <k.
[0073] As described above, the length of the outlet liner of a given outlet liner is less than or equal to the length of the outlet liner on which said particular liner is located. Generally, the length of (j + 1) -th egress lining is yj + 1% of the length of the j-th egress lining with 0 <yj + 1 <100. According to preferred embodiments of the present invention, the length of outlet liner of a particular outlet liner is less than the length of the outlet liner on which said outlet liner is located. Thus, preferably, 0 <yj + 1 <100. Even more preferably, the outlet liners will form a somewhat evenly-spaced "staggered" structure, depending on the length of the first outlet liner, a certain length of an additional outlet liner has a specific length. Namely, the length of (j + 1) -th eighth outlet is 100. (1 - j / (k + 1))% of the length of the first outlet lining.
[0074] Generally, as described above, the length of the first inlet coating is x% of the axial length of the substrate with 0 <x <100. If the catalyzed soot filter of the present invention contains at least one additional outlet coating , ie in total at least two outlet liners, the length of the first inlet liner is also chosen to form, together with the staggered structure of the outlet liners, a regular staggered pattern, with each of the steps having essentially the same length. Therefore, according to a preferred embodiment of the present invention, x is 100 / (k + 2).
[0075] If the catalytic soot filter of the present invention contains one or more additional outlet coatings, a given outlet coat may have the same chemical composition as that of one or all other outlet coatings. It is also possible that all output coatings have different chemical compositions.
[0076] It is preferred that at least one, preferably each of the other outlet coatings comprises an oxidation catalyst. Preferably, the oxidation catalyst contained in another outlet coating comprises at least one platinum group metal (PGM). More preferably, the oxidation catalyst contained in another outlet coating is selected from the group consisting of platinum, palladium, rhodium, iridium, and a mixture of two or more thereof.
[0077] Each outlet coating can contain the same or a different oxidation catalyst. More preferably, the oxidation catalyst of the at least one, preferably of each of the other outlet coatings consists of a mixture of platinum and palladium.
[0078] If the catalytic soot filter of the present invention contains two or more outlet coatings, it is preferred that the total outlet coatings, namely the k + 1 total outlet coatings comprise the oxidation catalyst in one amount from 5 to 100 g / ft3 (g / (30.48 cm) 3), more preferably from 7 to 90 g / ft3 (g / (30.48 cm) 3), more preferably from 8 to 80 g / ft3 (g / (30.48 cm) 3), more preferably from 9 to 70 g / ft3 (g / (30.48 cm) 3), preferably from 10 to 60 g / ft3 (g / (30.48 cm)) 3). As for the preferred embodiment in which the oxidation catalyst of the outlet coatings is at least a PGM component, the term "amount of oxidation catalyst" as used in the context of the present invention refers to the weight of the at least one PGM in the filter of final catalyzed soot, ie in the catalyzed soot filter after drying and calcination.
[0079] Furthermore, if the catalyzed soot filter of the present invention contains two or more outlet coatings, it is preferred that the proportion of PGM, defined as the amount of PGM contained in the first inlet coat (g / ft3 (g / (30.48 cm) 3) divided by the total amount of PGM contained in the k + 1 outlets (g / ft3 (g / (30.48 cm) 3) is within the range of 1:10 to 1: 2. The PGM ratio is preferably within the range of 1: 9 to 1: 2, more preferably from 1: 8 to 1: 3, and more preferably from 1: 7 to 1: 3., Preferably within the range of 1: 7 to 1: 3.
[0080] According to another embodiment, in case the catalyzed soot filter of the present invention contains two or more outlet coatings, it is preferred that the proportion of PGM, defined as the amount of PGM contained in the first inlet coat (g / ft3 (g / (30.48 cm) 3) divided by the total amount of PGM contained in the k + 1 outlets (g / ft3 (g / (30.48 cm) 3) is within the range of 2: 1 to 10: 1. The PGM ratio is preferably within the range of 2: 1 to 9: 1, more preferably 3: 1 to 8: 1, and most preferably 3: 1 to 7: 1.
[0081] As previously described, it is preferred that the first inlet coating and each of the outlet coatings in case the catalyzed soot filter of the present invention contains an oxidation catalyst which most preferably consist of the mixture of palladium and platinum. Typically, the weight ratio of Pt: Pd in the first outlet coating is within the range of 10: 1 to 1:10, preferably from 9: 1 to greater than 1: 1, more preferably from 8: 1 to 1, 1: 1, more preferably from 7: 1 to 1.2: 1, more preferably from 6: 1 to 1.3: 1, more preferably from 5: 1 to 1.4: 1, more preferably from 4: 1 to 1.5: 1, as previously described. In addition, it is preferred that the weight ratio of platinum: palladium in the k + 1 output coating is within the range of 10: 1 to 1:10, preferably from 9: 1 to greater than 1: 1, more preferably from 8 : 1 to 1.1: 1, more preferably from 7: 1 to 1.2: 1, more preferably from 6: 1 to 1.3: 1, more preferably from 5: 1 to 1.4: 1, most preferably from 4: 1 to 1.5: 1.
[0082] Therefore, the present invention also relates to a soot filter catalyzed as described previously, the first inlet coating and the k + 1 outlet coatings comprising an oxidation catalyst consisting of platinum and palladium, with the weight ratio of platinum: palladium in the first inlet coating is within the range of 10: 1 to 1:10, preferably from 4: 1 to 1.5: 1, and the weight ratio of platinum: palladium in the k + 1 output coating is within the range of 10: 1 to 1:10, preferably from 4: 1 to 1.5: 1.
[0083] It is also possible that in the k + 1 output coatings, only platinum or only palladium is contained (o).
[0084] According to a preferred embodiment of the present invention, at least one of the other outlet coatings, preferably each of the other outlet coatings comprises at least one porous support material. If a given other outlet coating comprises at least one porous material, it may contain the same or a different porous material compared to another outlet coating. Most preferably, all outlet coatings comprise at least one porous material. Although there are no specific restrictions, it is preferred that the porous support material contained in the other outlet coatings is a refractory metal oxide. More preferably, the porous support material of at least one other outlet coating, preferably of each of the other outlet coatings, is selected from the group consisting of alumina, zirconia, silica, titania, a rare earth metal oxide such as a cerium oxide, praseodymium, lanthanum, neodymium and samarium, silica-alumina, alumino-silicates, alumina-zirconia, alumina-chromium, alumina-rare earth metal oxide, titania-silica, titania-zirconia, titania-alumina, and a mixture of two or more of them. More preferably, the at least one porous support material is selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
Thus, the present invention also relates to a catalyzed soot filter as described above, with at least one, preferably each of the other outlet coatings comprising at least one porous support material, the at least one being porous. a porous support material from at least one, preferably from each of the other outlet coatings is preferably selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
[0086] Therefore, the present invention also relates to a catalyzed soot filter as described above, the first inlet and outlet coatings comprising at least one porous support material, the at least one porous support material. porous support of the first inlet coating is preferably selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of them, and the at least one porous support material of the outlet coatings is preferably selected of the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
[0087] According to a preferred embodiment, the refractory metal oxide of the first inlet coating and / or the outlet coatings essentially consists of alumina, more preferably gamma-alumina or activated alumina, such as gamma- or eta-alumina . Preferably, the activated alumina has an average surface area, determined according to the measurement of the BET surface area according to DIN 66131, from 60 to 300 m2 / g, preferably from 90 to 200 m2 / g, more preferably from 100 to 180 m2 / g.
[0088] According to an even more preferred embodiment of the present invention, each of the outlet coatings has the same chemical composition, ie in the process for preparing the catalyzed soot filter of the present invention, coating the flow substrate through the wall with the k + 1 output coatings it is carried out using a specific washcoat composition. Most preferably, all coatings, i.e. the first inlet coat and all outward coatings have the same chemical composition.
[0089] If the catalyzed soot filter of the present invention comprises one or more other outlet coatings, ie at least two outlet coatings, the first inlet coat and the outlet coatings are present on the flow substrate through wall at a coating loading ratio of less than 0.5, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: total loading of all outlet coatings [g / inch3 (g / (2.54 cm) 3)].
[0090] Regarding the process for manufacturing the catalyzed soot filter of the present invention comprising two or more outlet coatings, essentially the same process is carried out as described above for the catalyzed soot filter comprising only a first inlet coating . However, after step (iii), at least one other exit coating is applied over the first exit coating. Preferably, after the first inlet coat has been applied, optionally after a first drying and / or calcination, the second outlet coat is applied over the first outlet coat. If a third exit coating is applied, it is preferred, optionally after drying and / or calcining the filter containing the first and second exit coatings, to apply the third exit coating on the second exit coating. Therefore, the present invention also relates to a process as previously described, said process additionally comprising: (iv) after (iii) applying k other exit coatings, the (j + 1) -th exit coat is applied over the j-th output liner so that the (j + 1) -th egress coating extends from the end of the output to the end of the (j + 1) -th output liner, thereby defining the length of (j + 1) -th exit coat and the length of (j + 1) -th exit coat is yJ + 1% of the length of the j-th exit coat with 0 <yj + i <100; with k being an integer with k> 1, k preferably being within the range 1 to 4, more preferably 1 to 3; and where j is an integer with 1 <j <k.
[0091] More preferably, the (j + 1) -th eject coating is applied over the j-th egress coating so that the length of (j + 1) -th egress coating is 100. (1 - j / (k + 1))% of the length of the first exit coating.
[0092] Even more preferably, in (ii), the first inlet coating is applied so that x is 100 / (k + 2).
[0093] Regarding the typical and preferred methods of applying the other exit coatings, reference can be made to the typical and preferred methods as previously described for the application of the first exit coat. Regarding the typical and preferred conditions applied during the drying and / or calcination steps between or after the application of the individual outlet coatings, reference can be made to the typical and preferred conditions described above for drying and / or calcination of the first outlet liner.
[0094] The catalytic soot filter of the present invention can be used in an integrated emission treatment system, in particular an exhaust duct comprising one or more additional components for the treatment of diesel exhaust emissions. For example, such an exhaust duct which is much more preferably in fluid communication with the diesel engine may comprise a catalyzed soot filter according to the present invention and may additionally comprise a diesel oxidation catalyst (DOC) article and / or a selective catalytic reduction (SCR) article and / or a NOx reduction and storage catalytic article (NSR). Much more preferably, the DOC article and / or the SCR article and / or the NSR article are in fluid communication with the catalyzed soot filter. The diesel oxidation catalyst can be located upstream or downstream of the catalyzed soot filter and / or selective catalytic reduction component. More preferably, the catalyzed soot filter of the present invention is located downstream of the DOC article. Even more preferably the catalyzed soot filter of the present invention is located either upstream or downstream of the SCR article.
[0095] Therefore, the present invention also relates to a system for treating a diesel engine exhaust stream, the system comprising: an exhaust duct in fluid communication with the diesel engine via an exhaust manifold; the soot filter catalyzed as previously described; and one or more of the following in fluid communication with the catalyzed soot filter: a diesel oxidation catalyst (DOC) article; a selective catalytic reduction (SCR) article; a catalytic NOx storage and reduction (NSR) article.
[0096] An SCR article suitable for use in the exhaust duct is typically capable of effectively catalyzing the reduction of the NOx component contained in the diesel exhaust at temperatures below 600 ° C, so that adequate NOx levels can be treated even under conditions of low load typically associated with lower exhaust temperatures. Preferably, a suitable SCR article is capable of converting at least 50% of the NOx component to N2, depending on the amount of suitable reducer added to the system. Another desirable attribute for the SCR article is that it has the ability to catalyze the reaction of O2 with any excess of NH3 to N2 and H2O, so that NH3 is not emitted into the atmosphere. Useful SCR catalyst compositions used in the exhaust duct must also have thermal resistance at temperatures greater than 650 ° C. Such high temperatures can be found during regeneration of the upstream catalyzed soot filter. Suitable SCR articles are described, for example, in US 4,961,917 and US 5,516,497. Suitable SCR articles include one or both of an iron and copper promoter typically present in a zeolite in an amount of about 0.1 to 30 weight percent, preferably about 1 to 5 weight percent, of the total weight of the most zeolite promoter. In addition to their ability to catalyze the reduction of NOx with NH3 to N2, the disclosed SCR articles can also promote the oxidation of excess NH3 with O2, especially for those compositions having higher concentrations of promoter.
[0097] The exhaust gas treatment system of the present invention can additionally comprise a NOx storage (and optionally reduction) article. The NOx storage (and optionally reduction) article is preferably located downstream of the catalyzed soot filter.
[0098] Additionally, the present invention also relates to a method of treating a diesel engine exhaust stream, the exhaust stream containing soot particles, said method comprising contacting the exhaust stream with the catalyzed soot filter as described above. , optionally after having directed the exhaust stream through a diesel oxidation catalyst (DOC) article, said DOC article preferably comprising a flow through substrate or a flow substrate through wall. This method optionally additionally comprises directing the exhaust current resulting from the DOC article or the catalyzed soot filter through a selective catalytic reduction (SCR) article.
[0099] In the following, the present invention is further illustrated by the Examples.
Examples 1. Preparation of catalyst 1.1 Zonated catalyzed soot filter with an input / output coating washcoat loading ratio of 0.3 (Sample A, embodiment of the invention) [00100] For the input coating, 0.3 g / in3 (g / (2.54 cm) 3) of gamma-alumina was impregnated with an aqueous palladium nitrate solution giving a final dry Pd content of 10 g / ft3 (g / (30.48 cm) 3) followed by impregnation with a Platinum solution containing Platinum as an amine-stabilized Pt complex to give a dry Pt content of 20 g / ft3 (g / (30.48 cm) 3). The resulting powder was dispersed in water. Subsequently, the resulting slurry was used to coat the cordierite filter substrate (SiC, length: 6 inches = 15.24 cm; diameter: 5.66 inches = 14.38 cm) on the inlet side at 50% of the length total filter. After drying at 110 ° C in air and calcination at 450 ° C in air the amount of washcoat in 50% of the filter substrate entry was approximately 0.32 g / in3 (g / (2.54 cm) 3).
[00101] For the output coating 1.0 g / in3 (g / (2.54 cm) 3) of gamma-alumina was impregnated with an aqueous solution of Palladium nitrate giving a final dry Pd content of 5 g / ft3 (g / (30.48 cm) 3) followed by impregnation with a Platinum solution containing Platinum as an amine-stabilized Pt complex to a dry Pt content of 10 g / ft3 (g / (30.48 cm) ) 3). The resulting powder was dispersed in water. Subsequently, the resulting slurry was used to coat the cordierite filter substrate on the outlet side of the filter in 50% of the total length of the filter. After drying at 110 ° C in air and calcination at 450 ° C in air, the amount of washcoat in 50% of the filter substrate outlet was approximately 1.01 g / in3 (g / (2.54 cm) 3).
[00102] Thus, the proportion of coating loading was approximately 0.32. 1.2 Zonated catalyzed soot filter with a uniform washcoat loading ratio of inlet / outlet liner (Sample B, comparative example) [00103] For inlet liner 0.3 g / in3 (g / (2.54 cm) 3) gamma-alumina was impregnated with an aqueous solution of Palladium nitrate giving a final dry Pd content of 10 g / ft3 (g / (30.48 cm) 3) followed by an impregnation with a Platinum solution containing Platinum as an amine-stabilized Pt complex to give a dry Pt content of 20 g / ft3 (g / (30.48 cm) 3). The resulting powder was dispersed in water. Subsequently, the resulting slurry was used to coat the filter substrate (same substrate as in 1.1) on the inlet side for 50% of the total length of the filter. After drying at 110 ° C in air and calcination at 450 ° C in air the amount of washcoat in 50% of the filter substrate entry was approximately 0.32 g / in3 (g / (2.54 cm) 3).
[00104] For the output coating 0.3 g / in3 (g / (2.54 cm) 3) of gamma-alumina was impregnated with an aqueous solution of Palladium nitrate giving a final dry Pd content of 5 g / ft3 (g / (30.48 cm) 3) followed by impregnation with a Platinum solution containing Platinum as an amine-stabilized Pt complex to a dry Pt content of 10 g / ft3 (g / (30.48 cm) ) 3). The resulting powder was dispersed in water. Subsequently, the resulting slurry was used to coat the filter substrate on the filter outlet side for 50% of the total filter length. After drying at 110 ° C in air and calcination at 450 ° C in air the amount of washcoat in 50% of the filter substrate outlet was approximately 0.32 g / in3 (g / (2.54 cm) 3).
[00105] Thus, the proportion of coating loading was approximately 1.0. 2. Comparison of state-of-the-art catalyst technologies with the technology of the invention (Maximum soot loading test by regeneration test during idling) 2.1 Sample A (of the invention) [00106] Catalyzed soot filter zoned with a Inlet / outlet washcoat loading ratio of 0.32: - Inlet liner: 20 g / ft3 (g / (30.48 cm) 3) Pt, 10 g / ft3 (g / (30.48 cm) 3 ) Pd, 0.3 g / in3 (g / (2.54 cm) 3) of gamma-alumina - Outlet coating: 10 g / ft3 (g / (30.48 cm) 3) Pt, 5 g / ft3 (g / (30.48 cm) 3) Pd, 1.0 g / in3 (g / (2.54 cm) 3) of gamma-alumina 2.2 Sample B (comparative) [00107] Catalyzed soot filter zoned with a inlet / outlet liner washcoat loading ratio of approximately 1 (uniform washcoat load): - Inlet liner: 20 g / ft3 (g / (30.48 cm) 3) Pt, 10 g / ft3 (g / (30.48 cm) 3) Pd, 0.3 g / in3 (g / (2.54 cm) 3) gamma-alumina - Outlet coating: 10 g / ft3 (g / (30.48 cm) 3 ) Pt, 5 g / ft3 (g / (30.48 cm) 3) Pd, 0.3 g / in3 (g / (2.54 cm) 3) of gamma-alumina 3. Test procedures (Drop test for idling for SML) [00108] Samples A and B were tested for maximum temperature in regeneration test during drop to idle. The lower the maximum temperature and the gradient during regeneration during the fall to idle, the higher the soot load of the filter. Before testing, the samples were loaded with 5.5 g / L (= 5.5 g per L of substrate) of soot in a 4-cylinder light-weight diesel engine exhaust chain with a 2-liter engine capacity how to drive in a city at low speed.
[00109] For the regeneration test during a fall to idle, each sample was placed downstream in the exhaust line of a 4-cylinder light-weight diesel engine with a displacement of 2 L. The temperature in front of the catalyzed soot filter was raised to 620 ° C. When the temperature in the first thermocouple (1, cf. Fig. 3, distance from the CSF inlet side: 1 inch = 2.54 cm) of the catalyzed soot filter reached 650 ° C by soot regeneration, the engine was switched to idle mode. Higher temperatures and temperature gradients occurred at the rear of the CSF.
[00110] The positioning of thermocouples 1 to 4 in samples A and B for regeneration during drop to idle is shown in Fig. 3. The temperature versus time curves during the drop to idle test for the 4 thermocouples for samples A and B are shown in Fig. 4 and Fig.5, respectively. Sample A showed significantly lower maximum temperatures compared to sample B. Since the lower the temperature, the higher the soot mass limit, the maximum soot mass limit is higher for sample A. The maximum temperatures for Thermocouples in samples A and B of the catalyzed soot filter are shown in Table 1 below. The maximum temperature in the rear position on a 4 ”thermocouple of the catalyzed soot filter inlet is approximately 140 ° C lower for zoned catalyzed soot filter with an input / output coating washcoat loading ratio of 0.32: CLAIMS

权利要求:
Claims (27)
[1]
1. Catalytic soot filter, characterized in that it comprises: a substrate flowing through a wall comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the outlet end, and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; the inner walls of the inlet passages comprising a first inlet liner extending from the inlet end to an end of the first inlet liner, thereby defining a length of the first inlet liner, the length of the first liner of input is x% of the axial length of the substrate with 0 <x <100; the inner walls of the outlet passages comprising a first outlet liner extending from the outlet end to an end of the first outlet liner, thereby defining a length of the first outlet liner, the length of the first liner being output is 100-x% of the axial length of the substrate; the length of the first inlet liner defining an upstream zone and the length of the first outlet liner defining a downstream zone; the first inlet coating and the first outlet coating are present on the flow substrate through the wall in a coating loading ratio of 0.45 or less, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: loading the first outlet liner [g / inch3 (g / (2.54 cm) 3)]; wherein the first inlet coating comprises an oxidation catalyst comprising at least one platinum group metal (PGM) wherein the first outlet coating comprises an oxidation catalyst comprising at least one platinum group metal (PGM), in that the proportion of PGM, defined as the total amount of PGM contained in the first inlet coat [g / ft3 (g / (30.48 cm) 3)] divided by the total amount of PGM contained in the first outward coat [g / ft3 (g / (30.48 cm) 3)] is within the range of 2: 1 to 10: 1.
[2]
2. Catalytic soot filter according to claim 1, characterized in that the proportion of coating loading is within the range of 0.10 to 0.45, preferably from 0.20 to 0.40, more preferably from 0.30 to 0.35.
[3]
Catalytic soot filter according to claim 1 or 2, characterized in that x is within the range of 25 to 75, preferably from 35 to 65, more preferably from 45 to 55.
[4]
Catalytic soot filter according to any one of claims 1 to 3, characterized in that at least one platinum group metal (PGM) in the oxidation catalyst comprised in the first inlet coating is selected from the group consisting of platinum , palladium, rhodium, iridium, and a mixture of two or more of them, and the oxidation catalyst of the first inlet coating most preferably consists of a mixture of platinum and palladium.
[5]
Catalytic soot filter according to any one of claims 1 to 4, characterized in that the first inlet coating comprises oxidation catalyst in an amount of 5 to 100 g / ft3 (g / (30.48 cm) 3), preferably from 10 to 60 g / ft 3 (g / (30.48 cm) 3).
[6]
Catalytic soot filter according to any one of claims 1 to 5, characterized in that at least one metal of the platinum group (PGM) in the oxidation catalyst comprised in the first outlet coating is selected from the group consisting of platinum , palladium, rhodium, iridium, and a mixture of two or more of them, and the oxidation catalyst of the first outlet coating most preferably consists of a mixture of platinum and palladium.
[7]
Catalytic soot filter according to any one of claims 1 to 6, characterized in that the first outlet coating comprises oxidation catalyst in an amount of 5 to 100 g / ft3 (g / (30.48 cm) 3), preferably from 10 to 60 g / ft 3 (g / (30.48 cm) 3).
[8]
Catalytic soot filter according to any one of claims 1 to 7, characterized in that the proportion of PGM, defined as the total amount of PGM contained in the first inlet coating [g / ft3 (g / (30, 48 cm) 3)] divided by the total amount of PGM contained in the first outlet coating [g / ft3 (g / (30.48 cm) 3)] is within the range of 3: 1 to 7: 1.
[9]
Catalytic soot filter according to any one of claims 1 to 8, characterized in that the oxidation catalyst comprised in the first inlet coating and the first outlet coating respectively consists of platinum and palladium, the proportion in weight of platinum: palladium on the first inlet coating is within the range of 10: 1 to 1:10, preferably from 4: 1 to 1.5: 1, and the weight ratio of platinum: palladium on the first coating of output is within the range of 10: 1 to 1:10, preferably from 4: 1 to 1.5: 1.
[10]
Catalytic soot filter according to any one of claims 1 to 9, characterized in that the first inlet coating and the first outlet coating comprise at least one porous support material, the at least one porous support material. porous support of the first inlet liner is preferably selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same, and the at least one porous support material of the first outlet liner is preferably selected of the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
[11]
11. Catalytic soot filter according to any one of claims 1 to 10, characterized in that it additionally comprises k other exit coatings, the (j + 1) -th exit coat being located on the top of the j- th exit coating, said (j + 1) -th exit coat extending from the exit end to the (jt-1) -th exit coat, thereby defining the length of (j + 1) -th exit coat, the length of (j + 1) -th exit coat is yj + 1% of the length of the j-th exit coat with 0 <yj + 1 <100; with k being an integer with k> 1, k preferably being within the range 1 to 4, more preferably 1 to 3; and where j is an integer with 1 <j <k.
[12]
12. Catalytic soot filter according to claim 11, characterized in that the length of the (j + 1) -thim outlet coating is 100. (1 - j / (k + 1))% of the length of the first output coating.
[13]
13. Catalytic soot filter according to claim 11 or 12, characterized in that x is 100 / (k + 2).
[14]
Catalytic soot filter according to any one of claims 11 to 13, characterized in that at least one, preferably each of the other outlet coatings comprises an oxidation catalyst comprising at least one platinum group metal ( PGM), preferably selected from the group consisting of platinum, palladium, rhodium, iridium, and a mixture of two or more of them, and the oxidation catalyst being at least one, preferably from each of the other k exit coatings more preferably it consists of a mixture of platinum and palladium.
[15]
Catalytic soot filter according to any one of claims 11 to 14, characterized in that the total k + 1 outlet coatings comprise the oxidation catalyst in an amount of 5 to 100 g / ft3 (g / ( 30.48 cm) 3), preferably from 10 to 60 g / ft3 (g / (30.48 cm) 3).
[16]
16. Catalytic soot filter according to any one of claims 11 to 15, characterized in that the proportion of PGM, defined as the amount of PGM contained in the first inlet coating [g / ft3 (g / (30.48 cm ) 3)] divided by the total amount of PGM contained in the k + 1 outlet liners [g / ft3 (g / (30.48 cm) 3)] is within the range of 2: 1 to 10: 1, preferably within from 3: 1 to 7: 1.
[17]
17. Catalytic soot filter according to any one of claims 11 to 16, characterized by the fact that the oxidation catalyst comprised in the first inlet coating and the k + 1 outlet coatings respectively consist of platinum and palladium, the weight ratio of platinum: palladium in the first inlet coating is within the range of 10: 1 to 1:10, preferably from 4: 1 to 1.5: 1, and the weight ratio of platinum: palladium to k +1 output coating is within the range of 10: 1 to 1:10, preferably 4: 1 to 1.5: 1,
[18]
Catalytic soot filter according to any one of claims 11 to 17, characterized in that at least one, preferably each of the other outlet coatings comprises at least one porous support material, the at least one being porous support material of at least one, preferably of each of the other outlet coatings is preferably selected from the group consisting of Al2O3, ZrO2, CeO2, SiO2 and a mixture of two or more of the same.
[19]
19. Catalytic soot filter according to any one of claims 1 to 18, characterized in that the flow substrate through the wall has a porosity within the range of 38 to 75, determined according to a porosity measurement with mercury of according to DIN 66133, the substrate flowing through the wall is preferably a cordierite substrate or a silicon carbide substrate.
[20]
20. Catalytic soot filter according to any one of claims 1 to 19, characterized in that the loading of the first inlet coating is within the range of 0.1 to 1 g / inch3 (g / (2.54 cm) ) 3), preferably from 0.1 to 0.5 g / inch3 (g / (2.54 cm) 3).
[21]
21. Process for making a catalytic soot filter as defined in any one of claims 1 to 20, characterized in that it comprises: (i) providing a flow substrate through the wall, preferably having a porosity within the range of 38 to 75 , determined according to porosity measurement with mercury according to DIN 66133, said flow substrate through wall comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and the end of exit, and a plurality of passages defined by internal walls of the flow substrate through the wall; the plurality of passages comprising inlet passages having an open inlet end and a closed outlet end, and outlet passages having a closed inlet end and an open outlet end; (ii) applying the first inlet liner to the inner walls of the inlet passages such that the first inlet liner extends from the inlet end to the end of the first inlet liner by means of which a length of the first liner is defined input, the length of the first input coating being x% of the axial length of the substrate with 0 <x <100, thereby adjusting the loading of the first input coating to a predetermined value that is preferably within the range of 0, 1 to 1 g / inch3 (g / (2.54 cm) 3); (iii) before (ii) or after (ii), apply the first outlet liner to the inner walls of the outlet passages such that the first outlet liner extends from the outlet end to the end of the first outlet liner whereby a length of the first outlet liner is defined, the length of the first outlet liner being 100-x% of the axial length of the substrate, thereby adjusting the loading of the first outlet liner to a value such that the coating loading ratio, calculated as the loading ratio of the first inlet coating [g / inch3 (g / (2.54 cm) 3)]: loading the first outlet coating [g / inch3 (g / (2, 54 cm) 3)] is 0.45 or less, preferably within the range of 0.10 to 0.45, more preferably from 0.20 to 0.40, more preferably from 0.30 to 0.35; (iv) optionally after (iii), apply k other exit coatings, the (j + 1) -th exit coat being applied over the j-th exit coat so that the (j + 1) -th output liner extends from the output end to the end of the (j + 1) -th output liner, thereby defining the length of (j + 1) -the tenth output liner and the length of (j + 1) - th output liner is yj + 1% of the length of the j-th output liner with 0 <yj + i <100; with k being an integer with k> 1, k preferably being within the range 1 to 4, more preferably 1 to 3; and where j is an integer with 1 <j <k; wherein the first inlet coating comprises an oxidation catalyst comprising at least one platinum group metal (PGM) wherein the first outlet coating comprises an oxidation catalyst comprising at least one platinum group metal (PGM), in that the proportion of PGM, defined as the total amount of PGM contained in the first inlet coat [g / ft3 (g / (30.48 cm) 3)] divided by the total amount of PGM contained in the first outward coat [g / ft3 (g / (30.48 cm) 3)] is within the range of 2: 1 to 10: 1.
[22]
22. Process according to claim 21, characterized in that the (j + 1) -th eighth coating is applied over the j-th egress coating so that the length of (j + 1) -th coating output is 100. (1 - j / (k + 1))% of the length of the first output liner.
[23]
23. Process according to claim 21 or 22, characterized in that in (ii), the first inlet coating is applied so that x is 100 / (k + 2).
[24]
24. System for treating a diesel engine exhaust current, the system characterized by the fact that it comprises: an exhaust duct in fluid communication with the diesel engine via an exhaust manifold; catalyzed soot filter, as defined in any one of claims 1 to 20; and one or more of the following in fluid communication with the catalyzed soot filter: a diesel oxidation catalyst (DOC) article; a selective catalytic reduction (SCR) article; a catalytic NOx storage and reduction (NSR) article.
[25]
25. System according to claim 24, characterized by the fact that the catalyzed soot filter is positioned downstream of the DOC article and upstream or downstream of the SCR article.
[26]
26. Method for treating a diesel engine exhaust stream, the exhaust stream containing soot particles, said method characterized by the fact that it comprises contacting the exhaust stream with the catalyzed soot filter, as defined in any one of claims 1 to 20, optionally after having directed the exhaust stream through a diesel oxidation catalyst (DOC) article, said DOC article preferably comprising a flow through substrate or a flow substrate through wall.
[27]
27. Method according to claim 26, characterized in that it additionally comprises directing the exhaust current resulting from the DOC article or the catalyzed soot filter through a selective catalytic reduction (SCR) article.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-12-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|Free format text: O DEPOSITANTE DEVE RESPONDER A EXIGENCIA FORMULADA NESTE PARECER POR MEIO DO SERVICO DE CODIGO 206 EM ATE 60 (SESSENTA) DIAS, A PARTIR DA DATA DE PUBLICACAO NA RPI, SOB PENA DO ARQUIVAMENTO DO PEDIDO, DE ACORDO COM O ART. 34 DA LPI.PUBLIQUE-SE A EXIGENCIA (6.20). |

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2019-06-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-12-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2010, OBSERVADAS AS CONDICOES LEGAIS |

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2021-09-14| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |

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2022-01-04| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2645 DE 14-09-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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EP09176583|2009-11-20|

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PCT/EP2010/067914|WO2011061321A1|2009-11-20|2010-11-22|Zoned catalyzed soot filter|

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