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    • 专利摘要:
    filter for filtering particulate matter from a low-burning exhaust gas, and method for producing a filter. a method of producing a filter for filtering particulate matter from exhaust gas emitted from a low-combustion internal combustion engine, the filter of which comprises a porous substrate having inlet and outlet surfaces, in which the inlet surfaces are separated from the exit surfaces by a porous structure containing pores of a first medium pore size, where the entrance surfaces comprise a bridge network comprising interconnected particles of refractory material through the pores of the porous structure, the method of which comprises the step of contacting surfaces of inlet of the filter substrate with an aerosol comprising refractory material in the form of dry powder. the invention also relates to a filter obtainable by such a method.
    公开号:BR112012030599B1
    申请号:R112012030599
    申请日:2011-06-02
    公开日:2020-04-22
    发明作者:Vincent Twigg Martyn；Sutton Neal
    申请人:Johnson Matthey Plc；
    IPC主号:
    专利说明:

    (54) Title: FILTER FOR PARTICULAR MATTER FILTERING OF A POOR BURNING EXHAUST GAS AND METHOD TO PRODUCE A FILTER (51) Int.CI .: B01D 53/94; F01N 3/022; F01N 3/035.
    (30) Unionist Priority: 06/02/2010 US 61/350889.
    (73) Holder (s): JOHNSON MATTHEY PUBLIC LIMITED COMPANY.
    (72) Inventor (s): NEAL SUTTON; MARTYN VINCENT TWIGG.
    (86) PCT Application: PCT IB2011001205 of 06/02/2011 (87) PCT Publication: WO 2011/151711 of 08/12/2011 (85) Date of the Beginning of the National Phase: 11/30/2012 (57) Summary: FILTER FOR PARTICULAR MATTER FILTERING OF A POOR BURNING EXHAUST GAS, AND METHOD FOR PRODUCING A FILTER. A method of producing a filter to filter particulate matter from exhaust gas emitted from a low-combustion internal combustion engine, the filter of which comprises a porous substrate having inlet and outlet surfaces, in which the inlet surfaces are separated from the exit surfaces by a porous structure containing pores of a first medium pore size, wherein the entrance surfaces comprise a bridge network comprising interconnected particles of refractory material through the pores of the porous structure, the method of which comprises the step of contacting surfaces of inlet of the filter substrate with an aerosol comprising refractory material in the form of dry powder. The invention also relates to a filter obtainable by such a method.
    / 30 “FILTER FOR PARTICULAR MATTER FILTERING OF A POOR BURNING EXHAUST GAS, AND METHOD FOR PRODUCING A FILTER”
    FIELD OF THE INVENTION [001] The present invention relates to a filter to filter particulate matter from exhaust gas emitted from a low combustion internal combustion engine. In particular, the invention relates to an improvement of a filter comprising a porous substrate having inlet surfaces and outlet surfaces, wherein the inlet surfaces are separated from the outlet surfaces by a porous structure containing pores of a first pore size medium.
    BACKGROUND OF THE INVENTION [002] There are concerns about particulate matter (PM) emissions, commonly referred to as soot, from internal combustion engines and especially diesel engines in automotive applications operating in populated urban areas. The main concerns are associated with potential health effects and, more recently, with very tiny particles having sizes in the nanometer range. Nanoparticles around 100 nm in size are often referred to as a mode of accumulation, and very tiny particles, around 10 nm, as a mode of nucleation. Nanoparticles when inhaled can penetrate deep into the lungs, and can easily enter the bloodstream and travel to all the organs of the body, where they can cause a variety of problems. There is also evidence that nanoparticles can travel along the nerves of the olfactory glands directly into the animals' brains. Because of these concerns, the maximum amount of particulate emissions from the exhaust pipe of passenger cars and heavy-duty diesel vehicles is limited by legislation, which has decreased over the past few years in
    Petition 870190039486, of 26/04/2019, p. 6/38 / 30 compliance with the concern about environmental impact. Until recently, these emission limits were expressed in grams and the current European passenger car limit of 5 mg / km (Euro 5) requires exhaust gas filter equipment to achieve such low levels.
    [003] Diesel particulate filters (DPFs) were manufactured using a variety of materials, including sintered metal, ceramics or metal fibers, etc., with the most common type of real mass production being the flow type. wall made of porous ceramic material manufactured in the form of a monolithic arrangement of many small channels running along the length of the body. Alternative channels are plugged at one end, and then the exhaust gas is forced through the porous ceramic channel walls, which prevents most of the particulate from passing through, and then only filtered gas enters the environment. Ceramic wall flow filters in commercial production include those made from cordierite, various forms of silicon carbide and aluminum titanate. The actual shape and dimensions of the practical filters in vehicles, as well as properties, such as the channel wall thickness and its porosity, etc., depend on the application of interest.
    [004] The average pore dimensions of the filter channel walls, of a ceramic wall flow filter through which the gas passes, are typically in the range of 10 to 50 pm and generally around 20 pm. In striking contrast, the size of most of the diesel particulate matter of a modern high-speed diesel engine in a modern passenger car is much smaller, for example, 10 to 200 nm, so it must be able to pass through the filter unnoticed, and this is really what happens when exhaust gas passes through a clean filter for the first time. However, some PM is retained within the pore structure of the filter walls and it gradually builds up until the pores are bridged through a PM network, and this PM network then allows for the easy formation of a
    Petition 870190039486, of 26/04/2019, p. 7/38 / 30 particulate on the inner walls of the filter channels. The particulate cake is an excellent filtration medium and its presence provides very high filtration efficiency.
    [005] Periodically it is necessary to remove the trapped PM from a filtration to avoid the accumulation of excessive back pressure, which is detrimental to the engine's performance and can cause low fuel economy. Thus, in diesel applications, the trapped PM is removed from the filter by burning it in air in a process during which the amount of air available and the amount of excess fuel, used to obtain the high temperature necessary to ignore the Retained PM, are very carefully controlled. With respect to the end of this process, which is generally called regeneration, the removal of the last remaining particulate from the filter results in a marked decrease in the filtration efficiency and release of a burning of many small particles into the environment. Thus, filters have low filtration efficiency, when they are first used, and subsequently after each regeneration event, and also during the last part of each regeneration process.
    [006] Previously, the legislative limits for particulate emissions were on a weight basis and thus were propelled towards the largest and heaviest particles. A particle number measurement is now being introduced, which for diesel passenger cars is 6.0 x 1011, for new models from September 1, 2011 (Euro 5b limit values), and the same for Euro 5b limit values. Euro 6b limit (implementation data to be confirmed), and this has a propensity towards smaller, more environmentally dangerous particles. Another practical reason for this change is because the allowed particle mass has been progressively decreased and is now at a level where determining it by weighing very small masses is practically difficult. With the introduction of particle number legislation, it is very important to maintain efficiency
    Petition 870190039486, of 26/04/2019, p. 8/38 / 30 filtration at all times - emissions during regeneration and immediately afterwards can be a very significant contribution, in which everything is allowed and, as a result, current diesel filtration systems, in particular, are not suitable to meet new legislative requirements.
    [007] There is a problem with filters for spark ignition gasoline engines that operate at much higher temperatures than those prevailing in the exhaust gas of diesel engines, and especially those of diesel passenger cars. Here the temperature can be particulate matter so high that it is burned right after being trapped in the filter, thus a significant amount of particulate cake is never formed in the filter and high filtration efficiency is never achieved.
    [008] Catalytic filters are known for particular applications.
    For example, US Patent 4,477,417 (the entire content of which is incorporated herein by reference) describes a catalyst for reducing the ignition temperature of diesel soot.
    [009] There is therefore a primary need for a means of improving the filtration efficiency of the filters without causing additional back pressure to the filtration system.
    [0010] EP 2158956 (the entire content of which is incorporated by reference here) describes a hive filter of the type of wall flow, and a surface layer provided only on an inflow side partition wall or both on the side partition wall inflow as in the efflux side. The document specifically describes two embodiments of a honeycomb filter and five methods of manufacturing a honeycomb filter. The surface layer of the first or second honeycomb filter preferably carries fine particles of one or both of platinum and palladium and complies with the following conditions:
    (1) the peak pore diameter of the surface layer is equal
    Petition 870190039486, of 26/04/2019, p. 9/38 / 30 a or less than the average pore diameter of the base material of the partition wall, and the porosity of the surface layer is greater than that of the base material of the partition wall; (2) the surface layer has a peak pore diameter of 0.3 pm or more, and less than 20 pm, and a porosity of 60% or more, and less than 95% (measurement method is porosimetry mercury); (3) the L1 thickness of the surface layer is 0.5% or more, and less than 30% of the L2 thickness of the partition walls;
    (4) the mass of the surface layer per filtration area is 0.01 mg / cm 2 or more, and less than 6 mg / cm 2 , and (5) the partition wall base material has a diameter average pore size of 10 pm or more, and less than 60 pm, and a porosity of 40% or more, and less than 65%. The five methods of manufacturing a honeycomb filter comprise preparing a slurry comprising at least one fibrous material and applying the sludge to the honeycomb filter substrate by an atomization process, using, for example, an atomizer as a needle.
    [0011] The Society of Automotive Engineers (SAE) Technical Paper 2008-01-0621 of the World Congress, held in Detroit, Michigan, April 14-17, 2008, by the authors of EP 2158956, describes using a surface layer of material based on CeO2, having a particle size of 300 nm at a load of 15g / l (non-precious metal) in a silicon carbide diesel particulate filter.
    SUMMARY OF THE INVENTION [0012] Non-catalyzed coating filters have been investigated, having the surface layer described in EP 2158956, and have been found to be unsatisfactory standard reactive coating formulations for coating catalyzed soot filters that produce a coated filter that provides excessive back pressure in use; sun-based formulations were less durable and higher platinum group metal charges were inaccessible due to the difficulties of chemically depositing the metal.
    Petition 870190039486, of 26/04/2019, p. 10/38 / 30 [0013] It has now been found, very surprisingly, that by depositing a particulate refractory material in the form of an aerosol on the inlet surfaces of a filter to form a bridged network in it, the resulting filter can trap the same amount of particulate matter from an internal engine exhaust gas at a lower back pressure compared to a traditional filter, where a reactive coating permeates the porous structure of the filter.
    [0014] According to one aspect, the invention provides a method of producing a filter to filter particulate matter from the exhaust gas emitted from an internal combustion engine, preferably a low-burn diesel engine or a gas-injected engine from fuel, the filter of which comprises a porous substrate having inlet and outlet surfaces, in which the inlet surfaces are separated from the outlet surfaces by a porous structure containing pores of a first medium pore size, in which the inlet surfaces comprise a bridged network comprising interconnected particles of refractory material through the pores of the porous structure, the method of which comprises the step of contacting inlet surfaces of the filter substrate with an aerosol comprising refractory material in the form of dry powder.
    BRIEF DESCRIPTION OF THE DRAWINGS [0015] The invention can be more fully understood with reference to the accompanying drawings, in which:
    Figure 1 is a graph showing the filtration efficiency plotted over time for a prior art (comparative) catalyzed filter.
    Figure 2 is a graph showing the back pressure plotted in relation to the soot load for the same catalyzed filter of the previous technique (comparative).
    Figure 3 is like Figure 1, including an efficiency of
    Petition 870190039486, of 26/04/2019, p. 11/38 / 30 filtration versus time plotting also of the same catalyzed filter of the prior art (comparative), but now including the powder bridged network of refractory material according to the invention;
    Fig. 4 is like Figure 2, including a back pressure versus soot load plot also from the prior art (comparative) catalyzed filter, now including the refractory material powder bridge, according to the invention, after several filter loading / regeneration cycles;
    Fig. 5 is a graph showing the filtration efficiency plotted over time for a standard catalyzed SCR filter (prior art);
    Fig. 6 is a graph showing back pressure plotted in relation to the soot load for a standard catalyzed SCR filter (prior art);
    Fig. 7 is a graph comparing the filtration efficiency of the prior art SCR catalyzed filter, shown in Figure 5, with the same filter as the prior art, including powder of dry refractory material on the inlet surfaces, in accordance with the present invention. ;
    Fig. 8 is a graph comparing the soot-laden back pressure of the prior art SCR catalyzed filter, shown in Figure 6, with the same filter as the prior art, including dry refractory material powder on the inlet surfaces, according to the invention. ;
    Fig. 9 is a graph comparing the filtration efficiency of the prior art SCR catalyzed filter, shown in Figure 7, with the same filter as the prior art, including powder of dry refractory material on the inlet surfaces according to the present invention, both before and after engine aging;
    Fig. 10 is a graph comparing the soot-laden back pressure of the prior art SCR catalyzed filter, shown in Figure 8,
    Petition 870190039486, of 26/04/2019, p. 12/38 / 30 with the same filter of the prior art, including powder of dry refractory material on the intake surfaces, according to the present invention, both before and after the aging of the engine;
    Figure 11 is a graph comparing the filtration efficiency of a prior art SCR catalyzed filter with the same prior art filter, including dry catalyzed refractory material powder on the inlet surfaces according to the present invention;
    Fig. 12 is a graph comparing the soot-laden back pressure of a prior art SCR catalyzed filter with the same prior art filter, including dry catalyst refractory powder on the inlet surfaces according to the invention; and
    Figure 13 is a graph comparing the improvement of NOx conversion with and without the addition of catalyzed refractory material in a prior art SCR catalyzed filter.
    DETAILED DESCRIPTION OF THE INVENTION [0016] The present invention provides a means of improving the filtration efficiency of filters and, especially, wall flow filters, at all times while reducing back pressure, when the filter contains a given amount of particulate matter imprisoned. The filter can be a “bare” filter or with built-in catalytic function capability, such as oxidation, NOx uptake or selective catalytic reduction activity. It has been found that the introduction of a small amount of an appropriately fine inorganic refractory material to the inlet side of a wall flow filter in the form of a fine dry aerosol can result in improved filtration performance under all operating conditions, and it also provides the important benefit of decreasing back pressure in particulate loads supplied under operating conditions present in diesel engine and gasoline exhaust gas applications.
    [0017] It is believed that the mechanism by which inorganic material
    Petition 870190039486, of 26/04/2019, p. 13/38 / 30 added works the following properties of inorganic material are important variables:
    1. It can be of a suitable small size (less than 10 pm and preferably between 0.2 and 5.0 pm), so it can be applied to the inlet side of a filter as an aerosol in a flow of gas, preferably air;
    2. Its size may be such that it does not substantially enter the pores of the filter walls, and that it forms a bridged network through it. The actual optimum average size depends on the characteristics of the filter in question. In practice, it was found that the size can be greater than 0.2 pm, when using filters with average pore diameters around 15.0-20.0 pm.
    3. This bridged structure through the pores can be porous, in order to allow gas flow through it and to facilitate the development of particulate cake when exposed to exhaust gas. Expressing porosity in terms of apparent density powders before introduction as an aerosol, which well represents having apparent densities in the range of 0.1-0.6 g / cm 3 ;
    4. This inorganic material is sufficiently refractory to withstand high temperatures, such as those experienced during regeneration of diesel engines and episodes of fire failure in gasoline engines. Typically, it should have a melting point (softening temperature) above 1000 ° C;
    5. The surface texture can be such that the particles tend to intertwine and are not readily removed from the filter. This property is reflected, in part, in a low apparent density, referred to below.
    [0018] The bridge network for use of the present invention is different from a traditional reactive coating applied to a substrate monolith. In
    Petition 870190039486, of 26/04/2019, p. 14/38 / 30 a traditional reactive coating, discrete particles are deposited and the empty space in the reactive coating is defined, among others, by the density of the particles. In the bridged network of the present invention, the void space is formed by the interconnectivity of the particles, which interact to form the bridged network.
    [0019] It is relevant that the pore size of the filter material and the particle size of inorganic material are adapted for optimal performance. Thus, the size of a particular inorganic material that provides important results in one type of filter could be entirely unsuitable for use in a filter with a larger pore structure. The materials that work well have aerodynamic properties that facilitate the easy formation of an aerosol, and generally have apparent densities of less than 1 g / cm3 and, typically, in the range of 0.05 to 0.5 g / cm3 and, preferably, in the range of 0.1 to 0.4 g / cm3, where said bulk density is measured under conditions suitable for aerosol application and / or for application on the filter. The low apparent density shows that the particles of the material have a tendency to lock together, a necessary property when bridged through pore entries in the filter walls. The amount of material added to a filter of 14.4 cm in diameter and
    17.8 cm in length is typically 2 to 100 g and, preferably, 5 to 50 g, and pro rata quantities for different filter sizes.
    [0020] In embodiments, the refractory material can be based on an oxide selected from the group consisting of alumina, silica, zirconium dioxide, ceria, chromium oxide, magnesia, calcium oxide, titanium oxide and mixed oxides of any two or more of them. Alternatively, or in addition to, the refractory material may comprise a molecular sieve. The molecular sieve can be a silicate zeolite, an aluminosilicate zeolite, a metal-substituted aluminosilicate zeolite or a non-zeolite molecular sieve. Where the molecular sieve of
    Petition 870190039486, of 26/04/2019, p. 15/38 / 30 non-zeolite is not used, the or each non-zeolite molecular sieve can be an AIPO, a MeAIPO, a SAPO or a MeAPSO. Molecular sieves having the CHA structure are particularly preferred, such as SAPO-34 or SSZ-13.
    [0021] Greater advantages of the present invention include filters, which contain catalyst on the walls, which can be treated after they have been catalyzed and thus do not interfere with the process of introducing catalyst into the pores of the filter walls. In addition, no high temperature processing procedure is required that could be detrimental to the catalyst. Alternative procedures that treat the filter before the catalytic step can seriously hamper the application of catalyst and prevent this from being done to the extreme.
    [0022] Therefore, in the preferred embodiments, the filter substrate comprises a catalyst composition (known as a reactive coating) that penetrates the pore structure of the filter.
    [0023] The reactive coating for use in the filter of the invention is a catalytic reactive coating and, in embodiments, is selected from the group consisting of a hydrocarbon absorber, a three-way catalyst (TWC), a NOx absorber, a oxidation catalyst, a selective catalytic reduction (SCR) catalyst, a poor NOx catalyst, and combinations of two or more of the same. For example, in particular embodiments, inlet surfaces are coated with a reactive TWC coating or NOx absorber composition, and the outlet surfaces are coated with reactive SCR coating. In this arrangement, the intermittent rich operation of the engine, for example, to regenerate the NOx absorption capacity of the NOx absorber, can generate ammonia in situ in the TWC or NOx absorber for use in reducing NOx of SCR catalyst on the outlet surfaces. Similarly, an oxidation catalyst can include hydrocarbon absorber functionality. In
    Petition 870190039486, of 26/04/2019, p. 16/38 / 30 an embodiment, the inlet surfaces are not coated with SCR catalyst.
    [0024] The catalytic reactive coating, such as TWC, NOx absorber, oxidation catalyst, hydrocarbon absorber and the poor NOx catalyst, may contain one or more metals from the platinum group, particularly those selected from the group consisting of platinum , palladium and rhodium.
    [0025] TWCs are intended to catalyze three simultaneous reactions: (i) oxidation of carbon monoxide to carbon dioxide, (ii) oxidation of unburned hydrocarbons to carbon dioxide and water; and (iii) reduction of nitrogen oxides to nitrogen and oxygen. These three reactions occur most efficiently when the TWC is exhausted from an engine that runs at or near the stoichiometric point. As is well known in the art, the amount of carbon monoxide (CO), unburned hydrocarbons (HC) and nitrogen oxides (NOx), emitted when gasoline fuel is burned in a positive ignition internal combustion engine (for example, spark ignition), is predominantly influenced by the air to fuel ratio in the combustion cylinder. An exhaust gas having a stoichiometrically balanced composition is one in which the concentrations of oxidizing gases (NOx and O2) and reducing gases (HC and CO) are substantially equalized. The air-to-fuel ratio, which produces the stoichiometrically balanced exhaust gas composition, is typically given as 14: 7: 1.
    [0026] Theoretically, it should be possible to obtain complete conversion of O2, NOx, CO and HC into a stoichiometrically balanced exhaust gas composition in CO2, H2O and N2 and this is the service of the three-way catalyst. Ideally, therefore, the engine should be operated in such a way that the air-to-fuel ratio of the combustion mixture produces a stoichiometrically balanced exhaust gas composition.
    Petition 870190039486, of 26/04/2019, p. 17/38 / 30 [0027] One way of defining the compositional balance between oxidation gases and exhaust gas reduction gases is the lambda (λ) value of the exhaust gas, which can be defined according to equation (1 ) as:
    [0028] Air ratio for real engine fuel / Air ratio for stoichiometric engine fuel, (1) where a lambda value of 1 represents a stoichiometrically balanced (or stoichiometric) exhaust gas composition, where a lambda value of> 1 represents an excess of O2 and NOx and the composition is described as "poor", and where a lambda value of <1 represents an excess of HC and CO and the composition is described as "rich". It is also common in the art to refer to the air to fuel ratio in which the engine operates as “stoichiometric”, “poor” or “rich”, depending on the composition of the exhaust gas that the air to fuel ratio generates: stoichiometrically-operated gasoline or poorly burning gasoline engine.
    [0029] It should be noted that the reduction of NOx in N2 using a TWC is less efficient when the composition of the exhaust gas is of poor stoichiometry. Likewise, TWC is less able to oxidize CO and HC when the exhaust gas composition is rich. The challenge, therefore, is to keep the exhaust gas composition flowing into the TWC as close to the stoichiometric composition as possible.
    [0030] Naturally, when the engine is in a steady state it is relatively easy to ensure that the air to fuel ratio is stoichiometric. However, when the engine is used to propel a vehicle, the amount of fuel required changes transiently, depending on the load demand placed on the engine by the driver. This makes controlling the air-to-fuel ratio so that a stoichiometric exhaust gas is generated for three-way conversion particularly difficult. In practice, the air-to-fuel ratio is controlled by an engine control unit, which receives information about the gas composition of
    Petition 870190039486, of 26/04/2019, p. 18/38 / 30 exhaust from an exhaust gas oxygen sensor (EGO) (or lambda): a so-called closed loop feedback system. One aspect of such a system is that the air-to-fuel ratio fluctuates (or disturbs) between the stoichiometric point (or control setting) slightly rich and slightly poor, because there is a time delay associated with the air-to-adjustment fuel ratio. This disturbance is characterized by the amplitude of the air to fuel ratio and the frequency of response (Hz).
    [0031] The active components in a typical TWC comprise one or both platinum and palladium in combination with rhodium, or even only palladium (no rhodium), supported on a high surface area oxide, and an oxygen storage component .
    [0032] When the exhaust gas composition is slightly rich at the set point, there is a need for a small amount of oxygen to consume the unreacted CO and HC, that is, to make the reaction more stoichiometric. Conversely, when the exhaust gas circulates slightly poorly, excess oxygen needs to be consumed. This was achieved by developing the oxygen storage component that releases or absorbs oxygen during disturbances. The oxygen storage component (OSC) most commonly used in modern TWCs is cerium oxide (CeO2) or a mixed oxide containing cerium, for example, a mixed Ce / Zr oxide.
    [0033] NOx absorbing catalysts (NACs) are known, for example, from US Patent No. 5,473,887 (the entire contents of which are incorporated herein by reference) and are designed to adsorb nitrogen oxides (NOx) from the exhaust gas poor (lambda> 1) and to desorb NOx, when the oxygen concentration in the exhaust gas is decreased. Desorbed NOx can be reduced to N2 with a suitable reducer, for example gasoline fuel, promoted by a catalyst component, such as rhodium, from the NAC itself or located downstream from the NAC. In practice, control
    Petition 870190039486, of 26/04/2019, p. 19/38 / 30 of the oxygen concentration can be adjusted to a desired redox composition intermittently in response to a calculated remaining NOx adsorption capacity of NAC, for example, richer than normal (but still poor) engine operation operation of stoichiometry or lambda = 1 composition), stoichiometric or rich of stoichiometry (lambda <1). The concentration can be adjusted by numerous means, for example, throttling, injecting additional hydrocarbon fuel into an engine cylinder, such as during the exhaust stroke or injecting hydrocarbon fuel directly into the exhaust gas downstream of a pipe engine distribution.
    [0034] A typical NAC formulation includes a catalytic oxidation component, such as platinum, a significant amount, that is, substantially more than is required for use as a promoter, such as a promoter in a TWC of a storage component of NOx, such as barium, and a reduction catalyst, for example, rhodium. A commonly given mechanism for storing NOx from a poor exhaust gas for this formulation is:
    NO + / O.2> NO2 (2); and
    BaO + NO2 + / O.2> Ba (NO3) 2 (3), in which, in reaction (2), nitric oxide reacts with oxygen at the active oxidation sites of platinum to form NO2. The reaction (3) involves adsorption of NO2 by the storage material in the form of an inorganic nitrate.
    [0035] At lower concentrations of oxygen and / or at high temperatures, the nitrate species becomes thermodynamically unstable and decomposes, producing NO or NO2, according to reaction (4) below. In the presence of a suitable reducer, these nitrogen oxides are subsequently reduced by carbon monoxide, hydrogen and hydrocarbons in N2, which can occur through the reduction catalyst (see reaction (5)).
    Petition 870190039486, of 04/26/2019, p. 20/38 / 30
    BaíXOu-> BaO + 2NO + 3 A O2 or BaiXOj ··> BaO + 2NO2 + V O2 (4); and NO + CO> V N2 + CO2 (5);
    (other reactions include Ba (NO3) 2 + 8H 2 ^ BaO + 2NH3 + 5H2O followed by NH 3 + NOx ^ N 2 + yH 2 O or 2NH 3 + 2O 2 + CO ^ N 2 + 3H 2 O + CO 2 etc. .).
    [0036] In the reactions of (2) - (5) above, the reactive barium species is given as the oxide. However, it is understood that in the presence of air, most of the barium is in the form of carbonate or, possibly, hydroxide. The skilled person can adapt the reaction schemes above, consequently, for barium species other than oxide and sequence of catalytic coatings in the exhaust stream.
    [0037] Oxidation catalysts promote the oxidation of carbon monoxide to carbon dioxide and unburned hydrocarbons to carbon dioxide and water. Typical oxidation catalysts include platinum and / or palladium on a high surface area support.
    [0038] Hydrocarbon pickups typically include molecular sieves and can also be catalyzed, for example, with a platinum group metal, such as platinum or a combination of both platinum and palladium.
    [0039] SCR catalysts can be selected from the group consisting of at least one of Cu, Hf, La, Au, In, V, lanthanides and transition metals from Group VII, such as Fe, supported in a refractory oxide or molecular sieve . Suitable refractory oxides include A12O3, TiO2, CeO2, SiO2, ZrO2 and mixed oxides containing two or more of the same. The non-zeolitic catalyst can also include tungsten oxide, for example, V2O5 / WO3 / TiO2.
    [0040] Poor NOx catalysts, sometimes also called SCR hydrocarbon catalysts, DeNOx catalysts or even non-selective catalytic reduction catalysts, include Pt / Al2O3, Cu- Pt-, Fe-, Co- or Ir- ZSM -5 exchanged, protonated zeolites, such as
    Petition 870190039486, of 26/04/2019, p. 21/38 / 30 zeolites H-ZSM-5 or H-Y, perovskites and Ag / AEO3. In selective catalytic reduction (SCR) by hydrocarbons (HC), HC reacts with NOx instead of with O2 to form nitrogen, CO2 and water, according to equation (6):
    {HC} + NOx + CO2 + H2O (6) [0041] The competitive, non-selective reaction with oxygen is given by Equation (7):
    {HC} + O2 CO2 + H2O (7) [0042] Therefore, good HC-CR catalysts are more selective for reaction (6) than reaction (7).
    [0043] In particular embodiments, the reactive coating comprises at least one molecular sieve, such as an aluminosilicate zeolite or a SAPO, for positive ignition of PM uptake. The at least one molecular sieve can be a small, medium or large pore molecular sieve, for example. By "small pore molecular sieve" here, we mean molecular sieves containing a maximum ring size of 8, such as CHA; by "medium pore molecular sieve" here, we mean a molecular sieve containing a maximum ring size of 10, such as ZSM-5; and by "large pore molecular sieve" here, we mean a molecular sieve having a maximum ring size of 12, such as beta. Small pore molecular sieves are potentially advantageous for use in SCR catalysts - see, for example, WO 2008/132452 (the content of which is incorporated by reference here).
    [0044] The particular molecular sieves for application in the present invention are selected from the group consisting of AEI, ZSM-5, ZSM-20, ERI including ZSM-34, mordenite, ferrierite, BEA including Beta, Y, CHA, LEV including Nu- 3, MCM-22 and EU-1.
    [0045] In embodiments, molecular sieves can be non-metallized or metallized with at least one metal selected from the
    Petition 870190039486, of 26/04/2019, p. 22/38 / 30 group consisting of groups IB, IIB, IIIA, IIIB, VB, VIB, and VIII of the periodic table. Where metallized, the metal can be selected from the group consisting of Cr, Co, Cu, Fe, Hf, La, Ce, In, V, Mn, Ni, Zn, Ga and the precious metals Ag, Au, Pt, Pd and Rh. Such metallized molecular sieves can be used in a process to selectively catalyze the reduction of nitrogen oxides in positive ignition exhaust gas using a reducer. By "metallized" here, it is meant to include molecular sieves including one or more metals incorporated in a molecular sieve structure, for example, Fe in Beta structure and Cu in CHA structure. As mentioned above, where the reducer is a hydrocarbon, the process is sometimes called “selective hydrocarbon catalytic reduction (HC-SCR)”, “poor NOx catalysts” or “DeNOx catalysts”, and particular metals for this application include Cu , Pt, Mn, Fe, Co, Ni, Zn, Ag, Ce, Ga. The hydrocarbon reducer can be introduced into the exhaust gas by engine control techniques, for example, late post-injection or early post-injection (called “post-injection”).
    [0046] Where the reducer is a nitrogen reducer (called “NH3SCR”), metals of particular interest are selected from the group consisting of Ce, Fe and Cu. Suitable nitrogen reducers include ammonia. Ammonia can be generated in situ, for example, during rich regeneration of a NAC disposed upstream of the filter or by contacting a TWC with rich exhaust gas derived from the engine (see alternatives for reactions (4) and (5) above). Alternatively, the nitrogen reducer or a precursor can be injected directly into the exhaust gas. Suitable precursors include ammonia formate, urea and ammonia carbamate. The decomposition of the precursor into ammonia and other by-products can be by hydrothermal or catalytic hydrolysis.
    [0047] The methods of coating porous filter substrates are known to the skilled person and include, without limitation, the method described in
    Petition 870190039486, of 26/04/2019, p. 23/38 / 30
    WO 99/47260, that is, a method of coating a monolithic support comprising the steps of: (a) locating a retention medium on the top of a support, (b) dosing a predetermined amount of a liquid component in said media retention in the order (a) next (b), or (b) next (a), and (c) applying pressure or vacuum, removing said liquid component from within at least part of the support, and retaining substantially all said quantity inside the holder. Such process steps can be repeated from the other end of the monolithic support, then drying the first coating with optional burning / calcination.
    [0048] Other methods include that described in UK patent application No. 1000019.8 and entitled Coating a Monolith Substrate With Catalyst Component, filed on January 4, 2010, that is, a method of coating a beehive monolith substrate comprising a plurality channels with a liquid comprising a catalyst component, the method of which comprises the steps of: (i) containing a substantially and vertically hive monolith substrate; (ii) introducing a predetermined volume of liquid into the substrate, via open ends of the channels at a lower end of the substrate; (iii) sealingly retain the liquid introduced into the substrate; (iv) inverting the substrate containing the retained liquid; and (v) applying a vacuum to the open ends of the substrate channels in the lower inverted end of the substrate, to remove the liquid along the substrate channels. The viscosity of the reactive coating can be selected when appropriate. The particle size can be selected according to the average pore size of the porous filter structure. Thus, for wall flow filters having an average pore size of about 11 pm, a reactive coating having a D50 of 2.5 pm may be desirable, while for a wall flow filter having an average pore size of 22 pm, a 5 pm D90 may be more appropriate.
    Petition 870190039486, of 26/04/2019, p. 24/38 / 30 [0049] The reactive coating charge of the catalyst composition that penetrates the porous structure of the filter substrate will generally be less than 2.5g / in 3 (0.152 g / m 3 ) such as <2.0g / in 3 (0.122 g / m 3 ), 1.5 g / in 3 (0.0915 g / m 3 ), <1.3 g / in 3 (0.0793 g / m 3 ), 1.2 g / in 3 (0.0732 g / m 3 ), 1.1 g / in 3 (0.0671 g / m 3 ), 1.0 g / in 3 (0.061 g / m 3 ) or <0.8 g / in 3 (0.0488 g / m 3 ), etc.
    [0050] In other preferred embodiments, the bridged network comprises a catalyst. Such a catalyst can be selected from the group consisting of TWC, NOx, absorber, oxidation catalyst, hydrocarbon absorber, and the poor NOx catalyst may contain one or more metals from the platinum group, particularly those selected from the group consisting of platinum, palladium and rhodium. The particular embodiments comprise both a catalyst composition that penetrates the porous filter structure and a bridged network comprising a catalyst. Where both the porous filter structure and the bridged network comprise a catalyst composition, the catalysts in each of the porous filter structure and bridged network can be the same or different.
    [0051] The benefits of the invention can be obtained by loading powder of refractory material per unit volume less than 1.2 g / in 3 (0.0732 g / m 3 ), such as <1.0 g / in 3 ( 0.061 g / m 3 ), <0.8 g / in 3 (0.0488 g / m 3 ), <0.7 g / in 3 (0.0427 g / m 3 ), <0.6 g / in 3 (0.0366 g / m 3 ), <0.5 g / in 3 (0.0305 g / m 3 ), <0.3 g / in 3 (0.0183 g / m 3 ) etc.
    [0052] A filter in which the bridged network comprises a catalyst is advantageous for numerous reasons. Typically, a catalyst composition is coated by reactive coating on a filter substrate, so that the reactive coating penetrates the walls of the filter substrate. However, the pore structure of a filter substrate, such as a wall flow filter, is not perfect, and some reactive coating can become trapped in “closed-end pores”, where no catalytic activity is possible. This makes the catalyst, as a whole, a catalyst
    Petition 870190039486, of 26/04/2019, p. 25/38 / 30 less effective. By including the catalyst in the bridge network, the catalyst can be used more effectively. Thus, even when it is decided to include both a bridge network and a catalyst composition that penetrates the pore structure of the filter, less catalyst composition can be employed in the porous structure to obtain the same catalytic activity as a filter substrate of prior art, where the catalyst is completely located in the porous structure of the filter substrate.
    [0053] Another significant advantage is that the same catalytic activity can be obtained as a catalyst filter substrate of the prior art, without the same increase in back pressure. For example, EP 1663458 (the entire contents of which are hereby incorporated by reference) describes an SCR filter in which the filter is a wall flow monolith and in which an SCR catalyst composition penetrates the walls of the wall flow monolith. EP 1663458 generally describes that the walls of the wall flow filter may contain on or within them (i.e., not both) one or more catalytic materials. According to the description, "penetrate", when used to describe the dispersion of a catalyst slurry on the wall flow monolith substrate, means that the catalyst composition is dispersed through the substrate wall. The claims require a reactive coating load of 1.3 g / in 3 (0.0793 g / m 3 ). The present invention enables the same reactive coating loads at lower back pressure.
    [0054] In one embodiment, the catalyst - which penetrates the pore structure of the filter and / or comprises the bridged network - promotes the reduction of nitrogen oxides in an exhaust gas from an internal combustion engine with a low burn rate in the presence of a suitable reducer. Suitable reducers include hydrocarbons, such as engine fuel and nitrogen reducers, especially ammonia and its precursor urea. The process of catalytically reducing nitrogen oxides using a
    Petition 870190039486, of 26/04/2019, p. 26/38 / 30 reducer is called “selective catalytic reduction” or “SCR”. Processes employing a nitrogen reducer are particularly preferred.
    [0055] Surprisingly, the dust, when introduced into a wall flow filter, is retained and not easily shaken out. Without wishing to be bound by any theory, it is believed that this interconnection results from Van der Waals' forces. If, however, it is necessary to trap the powder in place, this can be done by treatment with, for example, polydimethylsiloxane, which, when hydrolyzed at a sufficiently high temperature, forms reactive silica, which can react with the powder, thus cementing the particles.
    [0056] The refractory materials described above can be inherently catalytic for particular processes. However, according to preferred embodiments, the refractory materials comprise a metal promoter selected from the group consisting of precious metals, Cr, Ce, Mn, Fe, Co, Ni and Cu and mixtures of any two or more thereof. Preferred catalysts include CuCHA, such as Cu-SAPO34, Cu-SSZ-13 and Fe-Beta zeolite, where Fe is present in the frame of the molecular sieve structure and / or otherwise associated, for example, ion- exchanged with the frame structure.
    [0057] The aerosol may comprise an additive to bind the interconnected particles together, after the filter, including the bridged mesh, is ignored, for example, the polydimethylsiloxane mentioned above.
    [0058] The porous substrate may be a metal, such as a sintered metal, or a ceramic, for example silicon carbide, cordierite, aluminum nitride, silicon nitride, aluminum titanate, alumina, mullite, for example, acite mullite (see, for example, WO 01/16050, the entire contents of which are incorporated by reference), polucite, a thermet (a mixture of a metal and a ceramic material that have been heat treated), such as Al2O3 / Fe, Al2O3 / Ni or B4C / Fe, or compound comprising segments of any two or more of them. In a
    Petition 870190039486, of 26/04/2019, p. 27/38 / 30 preferred embodiment, the filter is a wall flow filter comprising a porous ceramic filter substrate, having a plurality of input channels and a plurality of output channels, where each input channel and each outlet channel is defined, in part, by a porous structure ceramic wall, where each input channel is separated from an outlet channel by a porous structure ceramic wall. This filter arrangement is also described in SAE 810114 (the entire content of which is incorporated here by reference), and reference can be made to this document for other details. Alternatively, the filter may be a foam, or a so-called partial filter, such as those described in EP 1057519 (the entire contents of which are incorporated by reference) or WO 01/080978 (the entire contents of which are incorporated by reference).
    [0059] According to another aspect, the invention provides a filter obtainable by the method according to the invention. A method of obtaining a filter, according to the invention, is described in Example 2 above.
    [0060] According to another aspect, the invention provides a filter to filter particulate matter from the exhaust gas emitted from a low-combustion internal combustion engine, whose filter comprises a porous substrate having inlet and outlet surfaces, in that the inlet surfaces are separated from the outlet surfaces by a porous structure containing pores of a first medium pore size, in which the filter substrate comprises a catalyst composition that penetrates the porous structure of the filter and in which the inlet surfaces comprise a bridged network comprising interconnected particles of refractory material through the pores of the porous structure.
    [0061] The arrangement is such that, for an identical catalytic load expressed in weight per unit volume, for example, g / in 3 (1 g / in 3 = 0.061 g / m 3 ), the filter substrate, according to the present invention, has a lower back pressure in use than a filter comprising a catalyst charge
    Petition 870190039486, of 26/04/2019, p. 28/38 / 30 identical that penetrates a porous structure of the filter substrate defined by the inlet and outlet filter surfaces.
    [0062] According to another aspect, the invention provides the use of a filter, according to the invention, to treat exhaust gas from a low-combustion internal combustion engine, whose exhaust gas comprises particulate matter. In a preferred embodiment, the engine is used as the driving force for a vehicle.
    EXAMPLES
    Comparative Example 1 - Catalyzed Filter with Oxidation Catalyst No Refractory Material Added [0063] Exhaust gas containing particulate matter was obtained from a diesel particulate generator (DPG) operating on standard access yard pump diesel fuel containing a maximum of 50 ppm sulfur. This equipment was manufactured by Combustion Ltd and details of its design and mode of operation are provided in our European Patent 1850068 A1 (the entire contents of which are incorporated by reference). The DPG unit was operated with a mass gas flow rate of 250 kg / hour, a particulate generation rate of 10 g / hour with an in-line particulate silicon carbide filter maintained at around 240 ° C.
    [0064] The filter used was a standard production catalyzed silicon carbide filter made of cemented silicon carbide extruded segments (about 35 x 35 mm), having a circular cross section (14.4 cm in diameter) and 18 , 3 cm in length. The internal dimensions of the channel were 1.16 mm x 1.16 mm. The channel wall thickness was 0.305 mm and had a 45% porosity. The estimated average pore size of the mercury porosimetry measurements was 18 pm. The filter was catalyzed with different formulations of catalyst and two distinct zones along its length. The front, a 6.6 cm long zone, contained platinum and palladium in a 2 to 1 ratio, so that the total metallic charge
    Petition 870190039486, of 26/04/2019, p. 29/38 / 30 in this part of the filter was about 2.08g / l. The rear, 11.68 cm zone, also contained platinum and palladium in a 2 to 1 ratio, and the total metallic charge in this part of the filter was about 0.10 g / l. The filter was prepared according to the methods described in WO 99/47260 or UK patent application No. 1000019, as described above.
    [0065] During the loading of particulate matter in this filter, the gas flow rate was 250 kg / hour and the temperature was 240 ° C, and the back pressure was determined by a differential pressure sensor and recorded on a computer each 10 seconds. Particles passing through the filter were detected using a Combustion DMS 500 fast particle mass spectrometer, and particle size distributions were measured every second and recorded on a computer. Figure 1 shows the initial weak filtration efficiency of this filter, in terms of particle number, and how it gradually improves when increasing amounts of particulate matter were collected in the filter. After about 250 seconds, it was estimated that some 3 x 10 13 particles had passed through the filter. After a series regeneration of separate experiments on filters of the same type, using condensation particle counting (CPC) instruments, it was confirmed that the initial filtration efficiency was less than about 70%. Figure 2 shows the corresponding increase in back pressure through the filter when increasing amounts of particulate matter were retained in the filter, and that a disproportionately large part of the back pressure results from the accumulation of a relatively small amount of particulate matter in the filter.
    Example 2 - Catalyst Filter with Oxidation Catalyst With Refractory Material Added [0066] Dry powder zeolite (ZSM-1, 13 g), which was characterized by a Malvern Mastersizer 2000 as having an average particle size of about 2 qm in in the form of an aqueous dispersion, was distributed on the
    Petition 870190039486, of 26/04/2019, p. 30/38 / 30 inlet of the filter used in Example 1, after the trapped particulate matter has been completely removed by burning with air in an electric oven maintained at 650 ° C for 3 hours. The filter, into which the input surface bridged mesh was to be introduced, was arranged in the DPG device, which was carried out only in fan mode without fuel, that is, without generating diesel particulate, so that a flow of turbulent air entered the upstream side of the filter substrate. The zeolite was uniformly dispersed through the inlet side of the filter, adding it through a 250 mesh sieve in the upstream turbulent air flow, via a boss arranged in a duct enclosure upstream of the filter, thus forming an aerosol, that was transported into the filter. The particle size of the aerosol was determined to have a centralized distribution around 0.2 gm by the Combustion DMS 500, suggesting that in an aqueous dispersion there is considerable agglomeration of the primary particles. The filter was then loaded with particulate matter as in Example 1, using DPG. The filtration efficiency was monitored, as previously described, using a Combustion DMS 500, and the results shown in Figure
    3. The filtration efficiency has been dramatically improved compared to that without the addition of the zeolite powder. In addition, the backpressure versus particulate load curve was also dramatically lower compared to when no dust was present, and this effect was due to a lower increase in backpressure during the initial phase of particulate matter retention in the filter.
    [0067] The filter was then regenerated in air at 650 ° C for 3 hours in an electric oven and the process of loading particulate matter was repeated. The total loading of particulate matter and the regeneration cycle were repeated a total of three times, and the measured final filtration efficiency remained very high each time during the loading of particulate matter - within the experimental error, the filtration efficiency was
    Petition 870190039486, of 26/04/2019, p. 31/38 / 30 the same (more than 99%) that was during the first loading, after the zeolite powder was added inside the filter.
    [0068] Figure 4 shows the backpressure / particulate matter loading curve after several filter / regeneration loading cycles. The back pressure remained much lower than it was in the initial behavior without added powder. Thus, the small amount of this inorganic powder added dramatically improved the filtration efficiency and produced a highly desirable reduction in back pressure through the filter during normal use.
    Comparative Example 3 - Catalyzed Filter with Selective Catalytic Reduction Catalyst - No Refractory Material Added [0069] A silicon carbide filter with a circular cross section (diameter 14.4 cm) and a length of 15.24 cm, with a thickness of channel wall of 0.305 mm and a porosity of 42%, and an average pore size of 14 gm estimated by mercury porosimetry, was treated with a dispersion of SCR catalyst from zeolite ammonia to a small copper exchanged (2.5% by weight of copper), so that it contained 0.5 g / in 3 (0.0305 g / cm 3 ) in the channel walls for the entire length of the filter.
    [0070] The filter was then loaded with particulate matter as in Example 1, using a DPG. Changes in filtration and back pressure efficiency were monitored, as previously described, and the results shown in Figures 5 and 6, respectively.
    Comparative Example 4 - Catalyzed Filter with Selective Catalytic Reduction Catalyst with Refractory Material Added [0071] The same filter that was used in Comparative Example 3 was heated in an electric oven at 650 ° C to burn all the particulate matter and then when the zeolite cooled (11 g ZSM-5) it was uniformly dispersed as an aerosol across the inlet side of the filter, using the same method as described in Example 2. The
    Petition 870190039486, of 26/04/2019, p. 32/38 / 30 filtration and back pressure performance during loading with particulate matter were measured as previously and the results shown in Figures 7 and 8, respectively.
    [0072] The filter was then placed in the exhaust gas system of a 2-liter direct injection, Euro IV compatible, bench-mounted engine (suitable, for example, for a passenger car), downstream from a 1 liter oxidation catalyst (3.35 kg / m 3 with a 2: 1 weight ratio of platinum and palladium coated on a monolithic through-flow substrate of 350 cells per square inch), with the oriented filter of so that the treated powder channels were on the gas inlet side of the filter. The engine was operated using the two-step cycle as follows:
    [0073] Step 1: engine speed 3000 rpm, full load 290 Nm, duration 30 minutes, inlet gas temperature for oxidation catalyst was 560 ° C, gas temperature coming out of the oxidation catalyst and at the filter inlet was 545 ° C.
    [0074] Step 2: engine speed 1800 rpm, engine load 75 Nm, with post-injection of diesel fuel in cylinder, the duration was 30 minutes, inlet gas temperature for oxidation catalyst 490 ° C, and the gas temperature exiting the oxidation catalyst and at the filter inlet was 600 ° C.
    [0075] Standard Diesel fuel was used with a sulfur content of 50 ppm. Steps 1 and 2 were sequentially repeated for a total of 20 hours. The filter was then removed from the exhaust system and any particulate matter removed by treatment at 650 ° C and an electric oven for 3 hours. Using a DPG, the filtration and back pressure efficiency were monitored during loading of particulate matter, as previously described in Comparative Example 1, and the results shown in Figures 9 and 10, respectively.
    Petition 870190039486, of 26/04/2019, p. 33/38 / 30 [0076] The significant improvement in filtration and back pressure efficiency, obtained by adding zeolite, remained even after the filter aged in an engine for an equivalent of some 40,000 km.
    Comparative Example 5 - Catalytic Filter with Selective Catalytic Reduction Catalyst - with Catalyzed Refractory Material Added [0077] A filter with the same dimensions and SCR catalyst, as in Comparative Example 3, was tested in DPG and the performance of the filtration and back pressure efficiency it was found to be similar to that of Comparative Example 3. The particulate matter was then completely removed, burning in an electric oven at 650 ° C and then, when cooled, a mixture of zeolite cabazita (36 g) and zeolite ZSM5 ( 6 g) (no copper) exchanged for copper (2.5 wt% copper) was uniformly dispersed as an aerosol across the inlet surface side of the filter, using the same method as described in Example 2.
    [0078] The performance of the filtering efficiency and back pressure of the filter, before and after the addition of the catalyzed material, is shown in Figures 11 and 12, respectively.
    [0079] As well as obtaining significant improvements in both filtration efficiency and back pressure, the addition of catalyzed material serves to improve the NOx catalytic performance of the filter and this is shown in Figure 13. These results were obtained after poor hydrothermal aging at 800 ° C for 16 hours at 10% oxygen (O2), 10% water vapor, nitrogen balance (N2), and showed a marked improvement. The aged part was tested using the same engine installed as described in Example 4, placed with a urea injector to inject urea solution (AdBlue) into the exhaust gas, between the oxidation catalyst and the filter. Diesel fuel of <10 ppm sulfur was used. Following an initial phase, the engine ran on a series of engine loads in order to obtain a desired filter inlet temperature.
    Petition 870190039486, of 26/04/2019, p. 34/38 / 30
    The test conditions were as follows:
    [0080] "Alpha" is defined as the NH3 / NOX ratio. The position of the Exhaust Gas Recirculation valve programmed within the engine's engine control strategy has been suppressed in order to shut down EGR, so that steps 3-5, inclusive, were completed within a reasonable period of time (instead of hours). The entire series of steps 1 through 5 was carried out one immediately after the other.
    Step No. Filter inlet temperature(° C) Urea injection strategy Stage end point 1 450 Target 0.7 Alpha (EGR on) 2.5 minutes at a given evaluation point 2 400 Target 0.7 Alpha (EGR on) 2.5 minutes at a given evaluation point 3 300 Target 1.5 Alpha (EGR off) Detection of 20ppm of liquid ammonia at the filter outlet 4 250 Target 1.5 Alpha (EGR off) Detection of 20ppm of liquid ammonia at the filter outlet 5 220 Target 1.5 Alpha (EGR off) Detection of 20ppm of liquid ammonia at the filter outlet
    [0081] Referring to Figure 13, the peaks from left to right represent steps 1 to 5. It can be seen that in addition to the improved performance of the filtering efficiency and back pressure of the filter, before and after adding the catalyzed material, as shown in Figures 11 and 12, respectively, Figure 13 shows a marked improvement in NOx conversion activity compared to the filter in Comparative Example 3 (labeled "standard SCR filter").
    Petition 870190039486, of 26/04/2019, p. 35/38 / 2
    权利要求:
    Claims (5)
    [1]
    1/13 without bread

    [2]
    2/13

    [3]
    3/13

    [4]
    4/13

    [5]
    5/13
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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]|
    2019-02-26| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-11-12| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-03-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-04-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-05-12| B16C| Correction of notification of the grant|Free format text: REF. RPI 2572 DE 22/04/2020 QUANTO AO TITULO. |
    优先权:
    申请号 | 申请日 | 专利标题
    US35088910P| true| 2010-06-02|2010-06-02|
    PCT/IB2011/001205|WO2011151711A1|2010-06-02|2011-06-02|Diesel particulate filter|
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