Particulate filter
The use of plate-like crystals in the particulate filter enhances water resistance and filtration efficiency, improving initial filtration performance and reducing back pressure in gasoline engines.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- BASF MOBILE EMISSIONS CATALYSTS LLC
- Filing Date
- 2025-10-27
- Publication Date
- 2026-05-07
AI Technical Summary
Gasoline particulate filters suffer from deterioration in filtration efficiency due to water vapor condensation, leading to increased back pressure and reduced fresh filtration efficiency, particularly during the initial filtration phase.
A particulate filter with a layer of inorganic particles comprising plate-like crystals with an anti-agglomeration index of at least 50% is used in the inlet and/or outlet channels, optionally with an in-wall three-way conversion (TWC) coating, to enhance water resistance and maintain filtration efficiency.
The filter exhibits improved fresh filtration efficiency and resistance to water, maintaining low back pressure without significant increases, addressing the issues of condensation-related deterioration.
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Figure CN2025130120_07052026_PF_FP_ABST
Abstract
Description
PARTICULATE FILTERFIELD OF THE INVENTION
[0001] The present invention relates to a particulate filter, particularly a particulate filter for treatment of an exhaust stream from an internal combustion engine, which comprises an inorganic powder particle coating. The present invention also relates to an exhaust treatment system comprising the particulate filter and a method for treating an exhaust stream, particularly from an internal combustion engine.BACKGROUND OF THE INVENTION
[0002] Engine exhaust substantially consists of gaseous pollutants such as unburned hydrocarbons (HC) , carbon monoxide (CO) and nitrogen oxides (NOx) , and particulate matter (PM) . For gasoline engines, three-way conversion catalysts (hereinafter interchangeably referred to as TWC catalyst or TWC) for gaseous pollutants and filters for particulate matter (PM) are well-known exhaust treatment means to ensure the exhaust emission to meet emission regulations, such as including Euro 6 standards and China 6 standards.
[0003] In contrast to particulates generated by diesel lean burning engines, particulates generated by gasoline engines, such as gasoline direct-injection engines, tend to be finer and in lesser quantities. This is due to different combustion conditions of gasoline engines as compared to diesel engines. Also, hydrocarbon components are different in the emissions of gasoline engines as compared to diesel engines. Particulate filters specific for gasoline engines have been developed for a few decades in order to effectively treating the engine exhausts from gasoline engines.
[0004] For example, WO 2020 / 219376A1 describes a catalyzed particulate filter which comprises (1) a gasoline particulate filter (GPF) , (2) a major catalytic layer coated onto or within an inlet side, an outlet side, or both sides of the GPF surfaces, the major catalytic layer comprising a first composition which comprises a first support material and a first platinum group metal (PGM) , and (3) a minor functional material layer placed onto or within an inlet side, an outlet side, or both sides of the GPF surfaces, the minor catalytic layer comprising a second composition; wherein the major catalytic layer has a higher loading than the minor functional material layer, the minor functional material layer is placed on top of the major catalytic layer, or the major catalytic material layer is placed on top of the minor functional layer. The catalyzed particulate filter provides an improved catalytic efficiency in conjunction with an efficient filter.
[0005] WO2021 / 096841A1 describes a particulate filter for exhaust gas treatment from an internal combustion engine comprising (1) a particulate filter, the filter having an inlet side and an outlet side; (2) a functional material layer coated onto the inlet side, the outlet side, or both sides of the particulate filter. The functional material layer comprises (1) a first inorganic material comprises one or more of alumina, zirconia, ceria, silica, titania, a rare earth metal oxide other than ceria; and (2) a second inorganic material comprises one or more of alumina, zirconia, ceria, silica, titania, magnesium oxide, zinc oxide, manganese oxide, silicate zeolite, aluminosilicate zeolite.
[0006] WO2023 / 237052A1 describes a particulate filter, which comprises a substrate comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end; and a layer of inorganic particles loaded on surfaces of porous walls in the inlet channels and / or outlet channels, wherein the inorganic particles comprise or consist of boehmite particles.
[0007] Typically, the exhaust from a gasoline engine contains a large amount of water vapor originating from fuel combustion. The water vapor may potentially undergo condensation and become liquid water, which will make gasoline particulate filters, particular those having a layer of inorganic particles, suffer from serious deterioration of filtration efficiency. Original equipment manufacturers (OEMs) , i.e. the vehicle manufacturers, require gasoline particulate filters (GPFs) to have a high filtration efficiency at a Iow back pressure after water treatment, to avoid failure of particulate emission treatment due to existence of condensed water.
[0008] It is known that filtration performance of a gasoline particulate filter will improve over the lifetime of the filter, primarily as a result of ash and soot accumulation on the walls of the inlet sides in the filter. Also, it was identified that particulate number of an emission generated during the cold start phase of a test cycle represents the primary portion of the total particles emitted during the test. Therefore, the particle filtration performance at the initial filtration phase, also called fresh filtration efficiency, is a main concern for the study on filtration performance of gasoline particulate filters.
[0009] There is a need to provide a particulate filter for treatment of an exhaust stream from an internal combustion engine, particularly gasoline engine, which has improved water resistance, i.e., having improved fresh filtration efficiency after exposure to water as compared to prior particulate filters.SUMMARY OF THE INVENTION
[0010] The object of the present invention is to provide a particulate filter for treatment of an exhaust stream from an internal combustion engine, particularly a gasoline engine, which has improved fresh filtration efficiency after water treatment as compared to prior particulate filters, and preferably has a desirable back pressure.
[0011] It has been surprisingly found that the object of the present invention was achieved by a particulate filter comprising a layer of inorganic particles which comprises particles of plate-like crystals having an anti-agglomeration property in inlet channels and / or outlet channels of the filter.
[0012] Accordingly, in a first aspect, the present invention provides a particulate filter, which comprises -a substrate, comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0013] - a layer of inorganic particles loaded on surfaces of porous walls in the inlet channels and / or outlet channels, preferably in at least the inlet channels, which comprises inorganic particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0014] in which
[0015] M represents the anti-agglomeration index,
[0016] W1 represents initial weight of the sample,
[0017] W2 represents weight of dispersed inorganic particles,
[0018] P1 represents initial particle size D50 of the sample, and
[0019] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0020] and
[0021] - optionally, an in-wall three-way conversion (TWC) coating in the inlet channels and / or outlet channels.
[0022] In a second aspect, the present invention provides a method for producing a particulate filter, which includes
[0023] - providing a substrate comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0024] - optionally, applying a three-way conversion catalyst (TWC) coating in the porous walls in the inlet and / or outlet channels of the substrate,
[0025] - applying inorganic particles or precursors thereof on surfaces of porous walls in the inlet channels and / or outlet channels, wherein at least part of the inorganic particles or precursors thereof are particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0026] in which
[0027] M represents the anti-agglomeration index,
[0028] W1 represents initial weight of the sample,
[0029] W2 represents weight of dispersed inorganic particles,
[0030] P1 represents initial particle size D50 of the sample, and
[0031] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0032] and
[0033] - optionally, drying and / or calcining.
[0034] In a third aspect, the present invention provides an exhaust treatment system comprising a particulate filter as described in the first aspect or a particulate filter obtainable or obtained from the method as described in the second aspect, which is located downstream of an internal combustion engine, particularly a gasoline engine.
[0035] In a fourth aspect, the present invention provides a method for treating an exhaust stream from an internal combustion engine, particularly a gasoline engine, which includes contacting the exhaust stream with a particulate filter as described in the first aspect, a particulate filter obtainable or obtained from the method as described in the second aspect or an exhaust treatment system as described in the third aspect.
[0036] It has been found that the particulate filter according to the present invention exhibits an improved water resistance, in terms of improved fresh filtration efficiency after water treatment without no significant back pressure increase.BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Fig. 1 illustrates an external view of a wall-flow substrate having an inlet end and an outlet end.
[0038] Fig. 2 illustrates a longitudinal sectional view of an exemplary wall-flow substrate having a plurality of porous walls extending longitudinally from an inlet end to an outlet end of the substrate.
[0039] Figs. 3A, 3B, 3C and 3D show the XRD patterns of materials A, B, C and D respectively used for providing the layer of inorganic particles in Examples.
[0040] Fig. 4 shows the SEM images of material A, B, C and D respectively used for providing the layer of inorganic particles in Examples.
[0041] Fig. 5 shows the back pressure (BP) as measured for the particulate filters without in-wall TWC coating obtained from Examples respectively.
[0042] Fig. 6 shows the fresh filtration efficiency (FFE) as measured for the particulate filters without in-wall TWC coating obtained from Examples respectively.
[0043] Fig. 7 shows the back pressure (BP) as measured for the particulate filters with in-wall TWC coating obtained from Examples respectively.
[0044] Fig. 8 shows the fresh filtration efficiency (FFE) as measured for the particulate filters with in-wall TWC coating obtained from Examples respectively.DETAILED DESCRIPTION OF THE INVENTION
[0045] The present invention will be described in detail hereinafter. It is to be understood that the present invention may be embodied in many different ways and shall not be construed as limited to the embodiments set forth herein.
[0046] The singular forms “a” , “an” and “the” include plural referents unless the context clearly dictates otherwise. The terms “comprise” , “comprising” , etc. are used interchangeably with “contain” , “containing” , etc. and are to be interpreted in a non-limiting, open manner. That is, e.g., further components or elements may be present. The expressions “consists of” or cognates may be embraced within “comprises” or cognates.
[0047] The term “layer” , for example within the context of the layer of inorganic particles, is intended to mean a thin gas-permeable coating of materials carried on blank or pre-coated walls of a substrate. The layer may be in form of packed particles on walls of the substrate with gaps therebetween allowing for gas to permeate through.
[0048] The terms “D10” , “D50” and “D90” have their usual meanings, referring to the diameter points where the cumulative volume from the small-particle-diameter side reaches 10%, 50%and 90%in the cumulative particle size distribution respectively. The particle size distribution is measured by using a laser diffraction particle size distribution analyzer.
[0049] The term “plate-like” is intended to refer to a crystalline morphology approximating a plate-or flake-shaped crystal with an aspect ratio of at least 3, for example, at least 5.
[0050] The term “aspect ratio” used within the context of plate-like crystals is intended to refer to a ratio of the diameter to the thickness (diameter / thickness) of the plate-like crystals. The aspect ratio is determined by dividing the average crystal diameter by the average crystal thicknesses of the plate-like crystals. The average crystal diameter and the average crystal thickness may be obtained by observing a certain number of crystals (e.g., 100 crystals) via a scanning electron microscope and averaging respective values.
[0051] The term “crystal diameter” within the context of plate-like crystals is intended to refer to an equivalent diameter of a circle which has the same area as that of a main surface (i.e., the surface perpendicular to the thickness) of a plate-like crystal.
[0052] The term “particles of plate-like crystals” refers to particles which are aggregates or agglomerates of plate-like crystals and may also comprise single plate-like crystals.
[0053] The terms for platinum group metal (PGM) components, such as “palladium component” , “platinum component” and “rhodium component” are intended to describe the presence of respective platinum group metals in any possible valence state, which may be for example metal or metal oxide as the catalytically active form, or may be for example metal compound, complex or the like which, upon calcination or use of the catalyst, decomposes or otherwise converts to the catalytically active form.
[0054] The term “support” refers to a material in form of particles, for receiving and carrying one or more platinum group metal (PGM) components, and optionally one or more other components such as stabilizers, promoters and binders.
[0055] Herein, any reference to an amount of loading in the unit of “g / ft3” or “g / in3” is intended to mean the weight of the specified component, coating or layer per unit volume of the substrate or substrate part, on which they are carried.
[0056] According to the first aspect of the present invention, a particulate filter is provided, which comprises,
[0057] - a substrate, comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0058] - a layer of inorganic particles loaded on surfaces of porous walls in the inlet channels and / or outlet channels, which comprises inorganic particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0059] in which
[0060] M represents the anti-agglomeration index,
[0061] W1 represents initial weight of the sample,
[0062] W2 represents weight of dispersed inorganic particles,
[0063] P1 represents initial particle size D50 of the sample, and
[0064] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0065] and
[0066] - optionally, an in-wall three-way conversion (TWC) coating in the inlet channels and / or outlet channels.
[0067] In some embodiments, the particulate filter according to the present invention does not comprise the in-wall three-way conversion (TWC) coating.
[0068] In some other embodiments, the particulate filter according to the present invention comprises the in-wall three-way conversion (TWC) coating in the inlet channels and / or outlet channels. Particularly, the TWC coating is present in both inlet channels and outlet channels. Such particulate filters may also be referred to as FWC herein.
[0069] Preferably, according to the present invention, the inorganic particles of plate-like crystals have an anti-agglomeration index of at least 70%, more preferably 80%, most preferably 90%, in water. The process for determining the anti-agglomeration index will be described in detail hereinbelow in Examples.
[0070] The substrate as used herein refers to a structure that is suitable for withstanding conditions encountered in an exhaust stream from combustion engines, which can function as a particulate filter by itself, and can also carry functional materials, for example a filtration-improving layer such as a layer of inorganic particles as described herein, and optionally any other layer.
[0071] The substrate comprises a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels being inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels different from the inlet channels are outlet channels that are closed at the inlet end and open at the outlet end. The configuration of the substrate, also referred to as wall-flow substrate, requires the engine exhaust in the inlet channels flows through the porous walls into the outlet channels to reach the outlet end of the substrate.
[0072] Generally, the substrate may exhibit a honeycomb structure with alternate channels being blocked with a plug at opposite ends.
[0073] The porous walls of the substrate are generally made from ceramic materials or metal materials. Suitable ceramic materials useful for constructing the substrate may include any suitable refractory material, e.g., cordierite, mullite, cordierite-alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia, zirconium silicate, magnesium silicates, sillimanite, petalite, alumina, aluminum titanate and aluminosilicates. Typically, the porous walls of the substrate are made from cordierite or silicon carbide.
[0074] Suitable metallic materials useful for constructing the substrate may include heat resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component. Such alloys may contain one or more of nickel, chromium and aluminum, and the total amount of these metals may advantageously comprise at least 15%by weight of the alloy, for example 10 to 25%by weight of chromium, 3 to 8%by weight of aluminum, and up to 20%by weight of nickel. The alloys may also contain small or trace amounts of one or more metals such as manganese, copper, vanadium, titanium and the like. The surface of the metallic substrate may be oxidized at high temperature, e.g., 1000 ℃ or higher, to form an oxide layer on the surface of the substrate, improving the corrosion resistance of the alloy and facilitating adhesion of any coating or layer to the metal surface.
[0075] The channels at the closed ends are blocked with plugs of a sealant material. Any suitable sealant materials may be used without being limited.
[0076] The channels of the substrate can be of any suitable cross-sectional shape and size, such as circular, oval, triangular, rectangular, square, hexagonal, trapezoidal or other polygonal shapes. The substrate may have up to 700 channels (i.e. cells) per square inch of cross section. For example, the substrate may have 100 to 500 cells per square inch ( "cpsi" ) , typically 200 to 400 cpsi. The walls of the substrate may have various thicknesses, with a typical range of 2 mils to 0.1 inches. The substrate may have a porosity of from 40%to 80%, preferably 50%to 70%. Preferably, the substrate has a number of inlet channels that is equal to the number of outlet channels, and the channels are evenly distributed throughout the substrate.
[0077] Figs. 1 and 2 illustrate a typical wall-flow substrate comprising a plurality of inlet and outlet channels.
[0078] Fig. 1 depicts an external view of the wall-flow substrate having an inlet end (01) from which an exhaust stream (13) enters the substrate and an outlet end (02) from which the exhaust having been treated (14) exits. Alternate channels are blocked with plugs to form a checkerboard pattern at the inlet end (01) as shown and an opposing checkerboard pattern at the outlet end (02) which is not shown.
[0079] Fig. 2 schematically depicts a longitudinal sectional view of the wall-flow substrate, comprising a first plurality of channels (11) which are open at the inlet end (01) and closed at the outlet end (02) , and a second plurality of channels (12) which are open at the outlet end (02) and closed at the inlet end (01) . The channels are preferably parallel to each other to provide a constant wall thickness between the channels. The exhaust stream entering the first plurality of channels from the inlet end cannot leave the substrate without diffusing through the porous walls (10) into the second plurality of channels.
[0080] The particulate filter according to the present invention may comprise the layer of inorganic particles loaded on surfaces of the porous walls in the inlet channels and / or outlet channels. In other words, the layer of inorganic particles may be loaded on the porous walls in the inlet channels alone, in the outlet channels alone or in both inlet channels and outlet channels. Particularly, the layer of inorganic particles may be loaded on the porous walls in the inlet channels alone or in both inlet channels and outlet channels, more preferably in the inlet channels alone.
[0081] It will be appreciated that the layer of inorganic particles is intended to be loaded onto surfaces of the porous walls in the inlet and / or outlet channels, which is also referred to as “on-wall” coating, although a minor amount, for example less than 50%by weight, preferably less than 30%by weight, more preferably less than 10%by weight of inorganic particles may infiltrate into the pores within the porous walls.
[0082] According to the present invention, the inorganic particles may be particles of a non-PGM inorganic material. The non-PGM inorganic material may be for example alumina, hydrated alumina, boehmite, zirconia, ceria, silica, titania, magnesium oxide, zinc oxide, zinc carbonate, calcium oxide, calcium carbonate, silicate zeolite, aluminosilicate zeolite, or any combinations thereof.
[0083] Accordingly, the inorganic particles of plate-like crystals may be particles of plate-like crystals of a non-PGM inorganic material selected from alumina, hydrated alumina, boehmite, zirconia, ceria, silica, titania, magnesium oxide, zinc oxide, zinc carbonate, calcium oxide, calcium carbonate, silicate zeolite, aluminosilicate zeolite, or any combinations thereof.
[0084] Preferably, the inorganic particles, particularly the inorganic particles of plate-like crystals are particles of a non-PGM inorganic material selected from alumina, hydrated alumina, boehmite, silica, zinc oxide, zirconia or any combinations thereof, more preferably alumina, boehmite or any combinations thereof.
[0085] The layer of inorganic particles may optionally comprise a PGM component, such as palladium component and / or platinum component. The PGM component, if present, may be supported on the particles of plate-like crystals as mentioned above, or may be present separate from particles of plate-like crystals.
[0086] Herein, the layer of inorganic particles loaded on the porous walls in the inlet and / or outlet channels of the substrate particularly refers to a layer exhibiting minor or no, preferably no TWC activity, although it may exhibit a certain catalytic activity if one or more PGM components are comprised.
[0087] In some embodiments, the layer of inorganic particles does not comprise a PGM component. Preferably, the layer of inorganic particles may mainly or substantially consist of inorganic particles of plate-like crystals of a non-PGM inorganic material selected from alumina, hydrated alumina, boehmite, zirconia, ceria, silica, titania, magnesium oxide, zinc oxide, zinc carbonate, calcium oxide, calcium carbonate, silicate zeolite, aluminosilicate zeolite, or any combinations thereof, among which alumina, hydrated alumina, boehmite, silica, zinc oxide, zirconia, or any combinations thereof is preferable, with alumina, boehmite or any combinations thereof being more preferable.
[0088] Herein, any reference to “mainly consist of” within the context of the layer of inorganic particles is intended to mean the layer of inorganic particles comprise a major amount, i.e., more than 50%by volume, of the inorganic particles of plate-like crystals as specified, which may be for example 75%by volume or higher, 85%by volume or higher, 90%by volume or higher, or even 95%by volume or higher.
[0089] Herein, any reference to “substantially consist (s) of” within the context of the layer of inorganic particles is intended to mean the layer of inorganic particles comprises a non-intentionally adding amount of inorganic particles other than the inorganic particles of plate-like crystals as specified. Herein, the term “non-intentionally added amount” is intended to refer to no more than 1%by volume, no more than 0.5%by volume, no more than 0.1%by volume or no more than 0.05%by volume.
[0090] The plate-like crystals may have an average crystal diameter of no more than 20 microns (lm) , no more than 10 μm, no more than 5 μm, or no more than 3 μm, as measured by a scanning electron microscope (SEM) .
[0091] The plate-like crystals may have an average crystal thickness of no more than 1000 nanometers (nm) , no more than 500 nm, or no more than 300 nm, as measured by a scanning electron microscope (SEM) .
[0092] In some embodiments, the plate-like crystals may have an average crystal diameter of no more than 10 μm and an average crystal thickness of no more than 1000 nm, preferably an average crystal diameter of no more than 5 μm and an average crystal thickness of no more than 500 nm, more preferably an average crystal diameter of no more than 3 μm and an average crystal thickness of no more than 300 nm.
[0093] The plate-like crystals preferably have an aspect ratio (diameter / thickness ratio) of no more than 100, for example no more than 50, no more than 30, no more than 20, or no more than 15. Particularly, the plate-like crystals have an aspect ratio in the range of from 3 to 50, from 3 to 30, or from 3 to 20. Alternatively, the plate-like crystals have an aspect ratio in the range of from 5 to 50, from 5 to 30, or from 5 to 20, particularly 5 to 15.
[0094] There is no particular restriction to the geometry of the plate-like crystals. The main surface of the plate-like crystals, i.e., the surface perpendicular to the thickness, may have an irregular shape or have a regular shape, for example circular, oval and polygonal shapes, such as triangular, quadrangular and hexagonal.
[0095] The inorganic particles, particularly the inorganic particles of plate-like crystals, useful for the present invention may have a D90 of no more than 100 microns (lm) , no more than 50 μm, no more than 20 μm, or no more than 15 μm. The inorganic particles, particularly the inorganic particles of plate-like crystals, useful for the present invention may have a D50 in the range of from 1 to 30 μm, from 1 to 15 μm, or from 1 to 10 μm. The inorganic particles, particularly the inorganic particles of plate-like crystals, useful for the present invention may have a D10 of no more than 20 μm, no more than 8 μm, or no more than 4 μm.
[0096] The inorganic particles, particularly the inorganic particles of plate-like crystals, useful for the present invention may have a BET surface area of no more than 150 m2 / g, no more than 100 m2 / g, or no more than 50 m2 / g as determined by nitrogen adsorption.
[0097] Additionally or alternatively, the inorganic particles, particularly the inorganic particles of plate-like crystals, useful for the present invention may have a BET pore volume of no more than 0.5 cm3 / g, no more than 0.3 cm3 / g, or no more than 0.2 cm3 / g, as determined by nitrogen adsorption.
[0098] Generally, the particulate filter according to the present invention may comprise the layer of inorganic particles at a loading of from 1 to 500 g / L (i.e., about 0.016 to 8.19 g / in3) or from 2 to 300 g / L (i.e., about 0.033 to 4.92 g / in3) .
[0099] Particularly, the particulate filter according to the present invention which does not comprise the in-wall TWC coating may comprise the layer of inorganic particles at a loading of from 1 to 200 g / L (i.e., about 0.016 to 3.28 g / in3) , from 2 to 100 g / L (i.e., about 0.033 to 1.64 g / in3) , from 3 to 50 g / L (i.e., about 0.049 to 0.82 g / in3) , or from 10 to 40 g / L (i.e., about 0.16 to 0.66 g / in3) .
[0100] The particulate filter according to the present invention which comprises the in-wall TWC coating may comprise the layer of inorganic particles at a loading of from 1 to 500 g / L (i.e., about 0.016 to 8.19 g / in3) , from 2 to 200 g / L (i.e., about 0.033 to 3.28 g / in3) , from 5 to 100 g / L (i.e., about 0.082 to 1.64 g / in3) , or from 10 to 60 g / L (i.e., about 0.16 to 0.98 g / in3) .
[0101] The layer of inorganic particles may be applied onto the surfaces of the porous walls of the substrate by any known processes, such as dry coating process and washcoating process.
[0102] The dry coating process is well-known and generally carried out by blowing inorganic particles or suitable precursors thereof in particulate form by means of a carrier gas stream into channels of a substrate from the open ends, optionally drying and optionally calcining the coated substrate. By this process, no liquid carrier will be used. The inorganic particles are typically distributed on the surfaces of the porous walls of the channels in form of particle beds.
[0103] It will be appreciated that inorganic particles or suitable precursors thereof as applied will maintain their crystalline morphology after calcining the coated substrate. In other words, the calcining, if carried out, will not result in a change of the crystalline morphology of the inorganic particles.
[0104] In some embodiments, the inorganic particles or suitable precursors thereof may be blown into the inlet channels from the open ends towards the closed ends of the channels. The formed particle beds in the inlet channels may be located on the porous walls of the inlet channels, and also against the plug blocking the channels. The particle beds, i.e., the layer of inorganic particles is gas-permeable, which can contribute to trapping particulate matter (PM) of the exhaust stream and allow gaseous pollutants of the exhaust stream to permeate therethrough.
[0105] The layer of inorganic particles in form of particle beds may extend along the porous walls of the channels where the inorganic particles are loaded. It will be appreciated that the particle beds may extend along the entire length of the porous walls of the channels, or along only a part of the length of the porous walls of the channels.
[0106] The washcoating process is also well-known and generally carried out by coating a slurry comprising the inorganic particles or suitable precursors thereof and optional auxiliaries in a liquid solvent (e.g. water) into channels of a substrate from the open ends, drying and optionally calcining the coated substrate. The layer of inorganic particles applied by washcoating may be in the form of a porous coating, which may extend along the porous walls of the channels where the inorganic particles are loaded. Also, the porous coating may extend along the entire length of the porous walls of the channels, or along only a part of the length of the porous walls of the channels.
[0107] The in-wall TWC coating, when present, is typically in form of a washcoat comprising a TWC composition. The TWC coating may extend along the entire length of the porous walls of the channels, or along only a part of the length of the porous walls of the channels.
[0108] Herein, the term “in-wall” within the context of a TWC coating is intended to refer to a TWC coating with TWC components being intentionally loaded into pores of the porous walls of the substrate, although a minor amount, for example less than 50%by weight, preferably less than 30%by weight, more preferably less than 10%by weight of the TWC components may possibly be found on the surfaces of the porous walls in the coated channels. The meaning of the term “in-wall” is known in the art, for example as described in WO2017 / 109514A.
[0109] There is no particular restriction to the TWC composition useful for the TWC coating comprised in the particulate filter. Typically, the TWC composition comprises platinum group metal components as catalytically active species, e.g., rhodium component and one or both of platinum component and palladium component, which are supported on support particles. Useful materials as the support may be refractory metal oxides, oxygen storage components and any combinations thereof.
[0110] In some embodiments, the TWC composition comprises a rhodium component and a platinum component, which are supported on support particles. Preferably, the TWC composition is free or substantially free of a palladium component.
[0111] Examples of the refractory metal oxide may include, but are not limited to alumina, lanthana doped alumina, baria doped alumina, ceria doped alumina, zirconia doped alumina, ceria-zirconia doped alumina, lanthana-zirconia doped alumina, baria-lanthana doped alumina, baria-ceria doped alumina, baria-zirconia doped alumina, baria-lanthana-neodymia doped alumina, lanthana-ceria doped alumina, and any combinations thereof.
[0112] Examples of the oxygen storage component (OSC) may include, but are not limited to reducible rare earth metal oxides, such as ceria. The oxygen storage component may also comprise one or more of lanthana, praseodymia, neodymia, europia, samaria, ytterbia, yttria, zirconia and hafnia to constitute a composite oxide with ceria. Particularly, the oxygen storage component is selected from ceria-zirconia composite oxide and stabilized ceria-zirconia composite oxide.
[0113] In some further embodiments, the TWC composition comprises a rhodium component supported on particles of refractory metal oxide and a platinum component supported on particles of oxygen storage component.
[0114] The particulate filter according to the present invention may comprise the TWC coating at a loading of from 5 to 300 g / L (i.e., about 0.1 to 5.0 g / in3) , from 30 to 200 g / L (i.e., about 0.5 to 3.3 g / in3) , or from 50 to 150 g / L (i.e., about 0.8 to 2.5 g / in3) .
[0115] The in-wall TWC coating may comprise the PGM components at a total loading of 1.0 to 50.0 g / ft3 (i.e., about 0.04 to 1.8 g / L) , or 5.0 to 20.0 g / ft3 (i.e., about 0.18 to 0.71 g / L) , calculated as respective PGM elements.
[0116] The in-wall TWC coating may be applied onto the substrate by any known processes, typically by a washcoating process. The washcoating process is generally carried out by coating a slurry comprising TWC catalyst particles of supported PGM components and optionally auxiliaries in a solvent (e.g. water) , drying and calcining the coated substrate.
[0117] The in-wall TWC coating, when present, will be applied onto the substrate before loading the layer of inorganic particles as described hereinabove. The in-wall TWC coating, when present, may also be referred to as an under-layer coat, i.e., being applied before the layer of inorganic particles.
[0118] In some illustrative embodiments, the particulate filter according to the present invention comprises,
[0119] - a substrate, comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end, and
[0120] - a layer of inorganic particles loaded on surfaces of porous walls in at least the inlet channels, preferably in at least the inlet channels, which comprises inorganic particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0121] in which
[0122] M represents the anti-agglomeration index,
[0123] W1 represents initial weight of the sample,
[0124] W2 represents weight of dispersed inorganic particles,
[0125] P1 represents initial particle size D50 of the sample, and
[0126] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0127] wherein the particulate filter does not comprise an in-wall three-way conversion (TWC) coating.
[0128] In some other illustrative embodiments, the particulate filter according to the present invention comprises,
[0129] - a substrate, comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0130] - a layer of inorganic particles loaded on surfaces of porous walls in at least the inlet channels, preferably in at least the inlet channels, which comprises inorganic particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0131] in which
[0132] M represents the anti-agglomeration index,
[0133] W1 represents initial weight of the sample,
[0134] W2 represents weight of dispersed inorganic particles,
[0135] P1 represents initial particle size D50 of the sample, and
[0136] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0137] and
[0138] - an in-wall three-way conversion (TWC) coating in the inlet channels and outlet channels, which preferably comprises a rhodium component supported on particles of refractory metal oxide and a platinum component supported on particles of oxygen storage component.
[0139] In any illustrative embodiments as described above, the layer of inorganic particles mainly or substantially consists of inorganic particles of plate-like crystals of a non-PGM inorganic material selected from alumina, hydrated alumina, boehmite, silica, zinc oxide, zirconia, or any combinations thereof.
[0140] Preferably, in those illustrative embodiments, the layer of inorganic particles mainly or substantially consists of inorganic particles of plate-like crystals of a non-PGM inorganic material selected from alumina, hydrated alumina, boehmite, silica, zinc oxide, zirconia, or any combinations thereof, wherein the late-like crystals have an aspect ratio in the range of from 5 to 30, or from 5 to 20, particularly from 5 to 15.
[0141] In some particular embodiments, the layer of inorganic particles mainly or substantially consists of inorganic particles of plate-like crystals of a non-PGM inorganic material selected from alumina, hydrated alumina, boehmite, silica, or any combinations thereof, wherein the plate-like crystals have an aspect ratio in the range of from 5 to 20, or from 5 to 15.
[0142] In each of those illustrative and particular embodiments as described above, it is preferred that the inorganic particles of plate-like crystals have an anti-agglomeration index of at least 70%, more preferably 80%, most preferably 90%, in water.
[0143] In each of those illustrative and particular embodiments as described above, it is preferred that the inorganic particles substantially consist of inorganic particles of plate-like crystals having at least one, preferably all, of following particle size characteristics,
[0144] - D90 of no more than 20 pm,
[0145] - D50 of 1 to 15 pm, and
[0146] - D10 of no more than 8 pm.
[0147] It is more preferred that the inorganic particles substantially consist of inorganic particles of plate-like crystals having at least one, preferably all, of following particle size characteristics,
[0148] - D90 of no more than 15 pm,
[0149] - D50 of 1 to 10 pm, and
[0150] - D10 of no more than 4 pm.
[0151] In each of those illustrative and particular embodiments as described above, it is preferred that the layer of inorganic particles does not comprise a PGM component.
[0152] The particulate filter may be housed within a shell having an inlet and an outlet for an exhaust stream, that may be operatively associated and in fluid communication with other parts of an exhaust system of an engine.
[0153] According to the second aspect of the present invention, a method for producing a particulate filter is provided, which includes,
[0154] - providing a substrate comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0155] - optionally, applying a three-way conversion catalyst (TWC) coating in the porous walls in the inlet and / or outlet channels of the substrate,
[0156] - applying inorganic particles or precursors thereof on surfaces of porous walls in the inlet channels and / or outlet channels, wherein at least part of the inorganic particles or precursors thereof are particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0157] in which
[0158] M represents the anti-agglomeration index,
[0159] W1 represents initial weight of the sample,
[0160] W2 represents weight of dispersed inorganic particles,
[0161] P1 represents initial particle size D50 of the sample, and
[0162] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0163] and
[0164] - optionally, drying and / or calcining.
[0165] The inorganic particles may be applied on the surfaces of the porous walls by a dry coating or washcoating process as described hereinabove in the first aspect, preferably a dry coating process.
[0166] In some embodiments wherein the particulate filter comprises an in-wall TWC coating in the inlet and / or outlet channels of the substrate, the in-wall TWC coating is applied before applying the inorganic particles on surfaces of the porous walls. The TWC coating may be applied by a washcoating process as described hereinabove.
[0167] Any general description and preferences described hereinabove for the layer of inorganic particles and the in-wall TWC coating in the first aspect are applicable here by reference. In some embodiments, more than 50%by volume of the inorganic particles as applied, for example 75%by volume or higher, 85%by volume or higher, 90%by volume or higher, or even 95%by volume or higher, are inorganic particles of plate-like crystals as specified herein. Particularly, the inorganic particles as applied substantially consist of the inorganic particles of plate-like crystals as specified herein.
[0168] According to the third aspect, an exhaust treatment system is provided, which comprises a particulate filter as described in the first aspect or a particulate filter obtainable or obtained from the method as described in the second aspect, which is located downstream of a gasoline engine.
[0169] According to the fourth aspect, a method for treating an exhaust stream from a gasoline engine is provided, which includes contacting the exhaust stream with a particulate filter as described in the first aspect, a particulate filter obtainable or obtained from the method as described in the second aspect or an exhaust treatment system as described in the third aspect.
[0170] EMBODIMENTS
[0171] Various embodiments are listed below. It will be understood that the embodiments listed below may be combined with all aspects and other embodiments in accordance with the scope of the invention.
[0172] Embodiment 1. A particulate filter, which comprises
[0173] - a substrate, comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0174] - a layer of inorganic particles loaded on surfaces of porous walls in the inlet channels and / or outlet channels, which comprises inorganic particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0175] in which
[0176] M represents the anti-agglomeration index,
[0177] W1 represents initial weight of the sample,
[0178] W2 represents weight of dispersed inorganic particles,
[0179] P1 represents initial particle size D50 of the sample, and
[0180] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0181] and
[0182] - optionally, an in-wall TWC coating in the inlet channels and / or outlet channels.
[0183] Embodiment 2. The particulate filter according to Embodiment 1, which does not comprise the in-wall TWC coating.
[0184] Embodiment 3. The particulate filter according to Embodiment 1, which comprises the in-wall TWC coating in the inlet channels and / or outlet channels.
[0185] Embodiment 4. The particulate filter according to any of preceding Embodiments, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index of at least 70%, more preferably 80%, most preferably 90%, in water.
[0186] Embodiment 5. The particulate filter according to any of preceding Embodiments, wherein the layer of inorganic particles substantially consists of the inorganic particles of plate-like crystals.
[0187] Embodiment 6. The particulate filter according to any of preceding Embodiments, wherein the inorganic particles, particularly the inorganic particles of plate-like crystals, are particles of a non-PGM inorganic material, particularly selected from alumina, hydrated alumina, boehmite, zirconia, ceria, silica, titania, magnesium oxide, zinc oxide, zinc carbonate, calcium oxide, calcium carbonate, silicate zeolite, aluminosilicate zeolite, or any combinations thereof.
[0188] Embodiment 7. The particulate filter according to Embodiment 6, wherein the non-PGM inorganic material is selected from alumina, hydrated alumina, boehmite, silica, zinc oxide, zirconia, or any combinations thereof, preferably alumina, boehmite or a combination thereof.
[0189] Embodiment 8. The particulate filter according to any of preceding Embodiments, wherein the plate-like crystals have an average crystal diameter of no more than 20 μm, no more than 10 μm, no more than 5 μm, or no more than 3 μm, as measured by a scanning electron microscope (SEM) .
[0190] Embodiment 9. The particulate filter according to any of preceding Embodiments, wherein the plate-like crystals have an average crystal thickness of no more than 1000 nm, no more than 500 nm, or no more than 300 nm, as measured by a scanning electron microscope (SEM) .
[0191] Embodiment 10. The particulate filter according to any of preceding Embodiments, wherein the plate-like crystals have an aspect ratio of at least 3, for example at least 5, and no more than 100, for example no more than 50, no more than 30, no more than 20, or no more than 15.
[0192] Embodiment 11. The particulate filter according to any of preceding Embodiments, which comprises the layer of inorganic particles at a loading of from 1 to 500 g / L or from 2 to 300 g / L.
[0193] Embodiment 12. The particulate filter according to any of preceding Embodiments 1, 2 and 4 to 10, which comprises the layer of inorganic particles at a loading of from 1 to 200 g / L, from 2 to 100 g / L, from 3 to 50 g / L, or from 10 to 40 g / L.
[0194] Embodiment 13. The particulate filter according to any of preceding Embodiments 1 and 3 to 10, which comprises the layer of inorganic particles at a loading of from 1 to 500 g / L, from 2 to 200 g / L, from 5 to 100 g / L, or from 10 to 60 g / L.
[0195] Embodiment 14. The particulate filter according to any of preceding Embodiments, wherein the in-wall TWC coating is in form of a washcoat comprising a TWC composition, preferably comprising a rhodium component and a platinum component which are supported on support particles selected from refractory metal oxides, oxygen storage components and any combinations thereof, more preferably being free or substantially free of a palladium component.
[0196] Embodiment 15. The particulate filter according to any of preceding Embodiments, which is a gasoline particulate filter.
[0197] Embodiment 16. A method for producing a particulate filter as defined in any of Embodiments 1 to 15, which includes
[0198] - providing a substrate comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,
[0199] - optionally, applying a TWC coating in the porous walls in the inlet and / or outlet channels of the substrate,
[0200] - applying inorganic particles or precursors thereof on surfaces of porous walls in the inlet channels and / or outlet channels, wherein at least part of the inorganic particles or precursors thereof are particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,
[0201] in which
[0202] M represents the anti-agglomeration index,
[0203] W1 represents initial weight of the sample,
[0204] W2 represents weight of dispersed inorganic particles,
[0205] P1 represents initial particle size D50 of the sample, and
[0206] P2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,
[0207] and
[0208] -optionally, drying and / or calcining.
[0209] Embodiment 17. The method according to Embodiment 16, wherein the inorganic particles are applied by a dry coating or washcoating process, preferably by a dry coating process.
[0210] Embodiment 18. The method according to Embodiment 16 or 17, wherein the in-wall TWC coating is applied before applying the inorganic particles on surfaces of the porous walls.
[0211] Embodiment 19. An exhaust treatment system, which comprises a particulate filter according to any of Embodiments 1 to 15 or a particulate filter obtainable or obtained from the method according to any of Embodiments 16 to 18, and is located downstream of a gasoline engine.Embodiment 20. A method for treating an exhaust stream from a gasoline engine, which includes contacting the exhaust stream with a particulate filter according to any of Embodiments 1 to 15, a particulate filter obtainable or obtained from the method according to any of Embodiments 16 to 18, or an exhaust treatment system as defined in Embodiment 19.
[0212] EXAMPLES
[0213] Aspects of the present invention are more fully illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.
[0214] I. Materials and Characterization
[0215] Materials A to D, powders used for preparing the layer of inorganic particles in the particulate filters in Examples, are summarized in Table 1.
[0216] Particle sizes were measured by a Malvern 3000 laser diffraction particle size analyzer.
[0217] Surface area and pore volume were measured by a Micromeritics ASAP 2420 surface area and porosity analyzer with BET model under 77K nitrogen adsorption.
[0218] X-ray diffraction (XRD) scanning was measured by a Bruker D8 Advance. The XRD patterns of the materials A to D are shown in Figs. 3A to 3D, confirming that material A is alumina, materials B to D are boehmite.
[0219] SEM images of the materials are shown in Fig. 4, confirming that materials A and B are irregular agglomerates of small particles, and materials C and D are particles of plate-like crystals.
[0220] Anti-agglomeration index of the inorganic particles was determined in accordance with the following process. Firstly, 150 grams of pure water was poured into a separatory funnel that has passed the leak detection. Secondly, approximately 1.5 grams of a sample of inorganic particles having a particle size D50 measured as “P1” was weighed to obtain an accurate weight recorded as “W1” , and then slowly added into the separatory funnel. Thirdly, the separatory funnel was shaken in the same direction for 10 minutes, and then stood for 30 minutes. Fourthly, the powder phase and the solution phase were separated. The obtained solution phase was filtered using two layers of filter paper with pore size of 8 μm. The filter cake and the powder phase were dried in an oven at 110 ℃ for 5 hours. The dried filter cake without filter paper was weighed to obtain a weight recorded as “W2” . Fifthly, the dried filter cake and the dried powder phase were mixed and measured for the particle size D50 and recorded as “P2” . Finally, the anti-agglomeration index was calculated in accordance with the following equation:
[0221] Table 1
[0222] Table 1 (continued)
[0223] II. Methods for Characterization of Filtration Performance
[0224] II. 1 Back Pressure (BP)
[0225] The particulate filters of all the Examples were investigated for back pressure (BP) , as measured by a SuperFIow SF-1020 Flowbench under a cold air flow at 600 m3 / h.
[0226] II. 2 Fresh Filtration Efficiency (FFE)
[0227] The filtration efficiencies of the particulate filters of all Examples at fresh state (0 km, or out-of-box state) were measured, in accordance with the standard procedure defined in “BS EN ISO 29463-5: 2018 -Part 5: Test method for filter elements” , on a stationary air filter performance testing bench with a cold airflow at 600 m3 / h, using aerosol di (2-ethyl-hexyl) sebacate as particles. Particle number (PN) of particles ranging between 0.10 and 0.15 Im were recorded by a PN counter for both upstream and downstream of the filter being tested. The fresh filtration efficiency (FFE) was calculated in accordance with the equation.
[0228] III. Preparation of Particulate Filters
[0229] III. 1 Particulate Filters without in-wall TWC Coating
[0230] Reference Example 1-1 (R1-1)
[0231] A gasoline particulate filter cordierite substrate was used as a reference filter (blank filter) , which has a size of 132.1 mm (D) × 101.6 mm (L) , a volume of 1.4 L (about 85.4 in3) , a cell density of 200 cells per square inch (cpsi) , a wall thickness of 8 mils, a porosity of 55%as determined by a mercury intrusion measurement.
[0232] Reference Example 1-2 (R1-2)
[0233] A blank filter substrate after water treatment was provided.
[0234] A blank filter which is same as Reference Example 1-1 was placed horizontally in water at a depth of 2 cm for 10 minutes. Then, the blank filter was dried at a temperature of 200 ℃ for 4 hours.
[0235] Comparative Example 1-1 (C1-1)
[0236] A particulate filter having a layer of inorganic particles of material A was prepared.
[0237] A powder of material A was mixed with a carrier gas and blown into the inlet channels of a blank filter which is same as Reference Example 1-1 at a flow rate of 600 m3 / h at room temperature. The loading of the material A was 1 g / L (0.016 g / in3) .
[0238] Comparative Example 1-2 (C1-2)
[0239] A particulate filter having a layer of inorganic particles of material A after water treatment was provided.
[0240] A particulate filter which is same as Comparative Example 1-1 was subjected to the same water treatment as described in Reference Example 1-2.
[0241] Comparative Example 1-3 (C1-3)
[0242] A particulate filter having a layer of inorganic particles of material A was prepared.
[0243] A particulate filter was prepared by the same process as in Comparative Example 1-1, except that the loading of the material A was 3 g / L (0.049 g / in3) .
[0244] Comparative Example 1-4 (C1-4)
[0245] A particulate filter having a layer of inorganic particles of material A after water treatment was provided.
[0246] A particulate filter which is same as Comparative Example 1-3 was subjected to the same water treatment as described in Reference Example 1-2.
[0247] Comparative Example 1-5 (C1-5)
[0248] A particulate filter having a layer of inorganic particles of material A was prepared.
[0249] A particulate filter was prepared by the same process as in Comparative Example 1-1, except that the loading of the material A was 5 g / L (0.082 g / in3) .
[0250] Comparative Example 1-6 (C1-6)
[0251] A particulate filter having a layer of inorganic particles of material A after water treatment was provided.
[0252] A particulate filter which is same as Comparative Example 1-5 was subjected to the same water treatment as described in Reference Example 1-2.
[0253] Comparative Example 1-7 (C1-7)
[0254] A particulate filter having a layer of inorganic particles of material B was prepared.
[0255] A powder of material B was mixed with a carrier gas and blown into the inlet channels of a blank filter which is same as Reference Example 1-1 at a flow rate of 600 m3 / h at room temperature. The loading of the material B was 1 g / L (0.016 g / in3) .
[0256] Comparative Example 1-8 (C1-8)
[0257] A particulate filter having a layer of inorganic particles of material B after water treatment was provided.
[0258] A particulate filter same as Comparative Example 1-7 was subjected to the same water treatment as described in Reference Example 1-2.
[0259] Comparative Example 1-9 (C1-9)
[0260] A particulate filter having a layer of inorganic particles of material B was prepared.
[0261] A particulate filter was prepared by the same process as in Comparative Example 1-7, except that the loading of the material B was 3 g / L (0.049 g / in3) .
[0262] Comparative Example 1-10 (C1-10)
[0263] A particulate filter having a layer of inorganic particles of material B after water treatment was provided.
[0264] A particulate filter same as Comparative Example 1-9 was subjected to the same water treatment as described in Reference Example 1-2.
[0265] Comparative Example 1-11 (C1-11)
[0266] A particulate filter having a layer of inorganic particles of material B was prepared.
[0267] A particulate filter was prepared by the same process as in Comparative Example 1-7, except that the loading of the material B was 5 g / L (0.082 g / in3) .
[0268] Comparative Example 1-12 (C1-12)
[0269] A particulate filter having a layer of inorganic particles of material B after water treatment was provided.
[0270] A particulate filter which is same as Comparative Example 1-11 was subjected to the same water treatment as described in Reference Example 1-2.
[0271] Comparative Example 1-13 (C1-13)
[0272] A particulate filter having a layer of inorganic particles of material C was prepared.
[0273] A powder of material C was mixed with a carrier gas and blown into the inlet channels of a blank filter which is same as Reference Example 1-1 at a flow rate of 600 m3 / h at room temperature. The loading of the material C was 10 g / L (0.164 g / in3) .
[0274] Comparative Example 1-14 (C1-14)
[0275] A particulate filter having a layer of inorganic particles of material C after water treatment was provided.
[0276] A particulate filter which is same as Comparative Example 1-13 was subjected to the same water treatment as described in Reference Example 1-2.
[0277] Comparative Example 1-15 (C1-15)
[0278] A particulate filter having a layer of inorganic particles of material C was prepared.
[0279] A particulate filter was prepared by the same process as in Comparative Example 1-13, except that the loading of the material C was 15 g / L (0.246 g / in3) .
[0280] Comparative Example 1-16 (C1-16)
[0281] A particulate filter having a layer of inorganic particles of material C after water treatment was provided.
[0282] A particulate filter which is same as Comparative Example 1-15 was subjected to the same water treatment as described in Reference Example 1-2.
[0283] Comparative Example 1-17 (C1-17)
[0284] A particulate filter having a layer of inorganic particles of material C was prepared.
[0285] A particulate filter was prepared by the same process as in Comparative Example 1-13, except that the loading of the material C was 20 g / L (0.328 g / in3) .
[0286] Comparative Example 1-18 (C1-18)
[0287] A particulate filter having a layer of inorganic particles of material C after water treatment was provided.
[0288] A particulate filter which is same as Comparative Example 1-17 was subjected to the same water treatment as described in Reference Example 1-2.
[0289] Inventive Example 1-1 (E1-1)
[0290] A particulate filter having a layer of inorganic particles of material D was prepared.
[0291] A powder of material D was mixed with a carrier gas and blown into the inlet channels of a blank filter which is same as Reference Example 1-1 at a flow rate of 600 m3 / h at room temperature. The loading of the material D was 10 g / L (0.164 g / in3) .
[0292] Inventive Example 1-2 (E1-2)
[0293] A particulate filter having a layer of inorganic particles of material D after water treatment was provided.
[0294] A particulate filter which is same as Inventive Example 1-1 was subjected to the same water treatment as described in Reference Example 1-2.
[0295] Inventive Example 1-3 (E1-3)
[0296] A particulate filter having a layer of inorganic particles of material D was prepared.
[0297] A particulate filter was prepared by the same process as in Inventive Example 1-1, except that the loading of the material D was 20 g / L (0.328 g / in3) .
[0298] Inventive Example 1-4 (E1-4)
[0299] A particulate filter having a layer of inorganic particles of material D after water treatment was provided.
[0300] A particulate filter which is same as Inventive Example 1-3 was subjected to the same water treatment as described in Reference Example 1-2.
[0301] Inventive Example 1-5 (E1-5)
[0302] A particulate filter having a layer of inorganic particles of material D was prepared.
[0303] A particulate filter was prepared by the same process as in Inventive Example 1-1, except that the loading of the material D was 30 g / L (0.492 g / in3) .
[0304] Inventive Example 1-6 (E1-6)
[0305] A particulate filter having a layer of inorganic particles of material D after water treatment was provided.
[0306] A particulate filter which is same as Inventive Example 1-5 was subjected to the same water treatment as described in Reference Example 1-2.
[0307] The particulate filters as prepared in above Examples were tested for the Filtration Performance with respect to the back pressure (BP) and the fresh filtration efficiency (FFE) in accordance with the methods as described hereinabove. The test results for the particulate filters are summarized in Table 2 below.
[0308] Table 2
[0309] It shall be noted that the inorganic particles from materials A and B were loaded at amounts much lower than those of materials C and D, that is because a loading of material A and B at the same level of materials C and D will result in an unacceptable high back pressure.
[0310] The particulate filters of above Examples will be classed into two groups for better understanding the benefit of the layer of inorganic particles of plate-like crystals having the required anti-agglomeration index on the filter performances.
[0311] Group 1-I
[0312] This group includes particulate filters R1-1, C1-1, C1-3, C1-5, C1-7, C1-9, C1-11, C1-13, C1-15 and C1-17, E1-1, E1-3 and E1-5 respectively. The backpressure (BP) and fresh filtration efficiency (FFE) of those particulate filters are shown in Figs. 5 and 6 respectively.
[0313] It can be seen from the comparison of C1-1, C1-3, C1-5, C1-7, C1-9, C1-11, C1-13, C1-15, C1-17, E1-1, E1-3 and E1-5 with the blank filter R1-1, the fresh filtration efficiency (FFE) can be improved by applying a layer of inorganic particles onto the porous walls of the inlet channels of the substrate with an acceptably Iow increase of back pressure. The FFE of those particulate filters having a layer of organic particles ranges from 76%to almost 100%.
[0314] Group 1-II
[0315] This group includes particulate filters of R1-2, C1-2, C1-4, C1-6, C1-8, C1-10, C1-12, C1-14, C1-16 and C1-18, E1-2, E1-4 and E1-6, which correspond to the particulate filters of Group 1-I respectively but have been subjected to water treatment. The backpressure (BP) and fresh filtration efficiency (FFE) of this group of particulate filters are also shown in Figs. 5 and 6, respectively.
[0316] The influences of different inorganic particles on the water resistance of the particulate filters can determined from the comparison between corresponding particulate filters of group 1-I and group 1-II.
[0317] The particulate filters having a layer of inorganic particles of material A or B all exhibited a great decrease of FFE after water treatment. The FFE of those particulate filters decreases to a level between 60%and 70%. Those particulate filters did not exhibit acceptable water resistance, and the FFE improvement resulted from applying a layer of inorganic particles on a blank filter materially lost due to water treatment. The particulate filters having a layer of inorganic particles of material C retained a relatively high level of FFE between 81%to 90%after water treatment, which is however significantly lower than the FFE between 96%to 99.6%before water treatment. On the one hand, the material C, i.e., inorganic particles of plate-like crystals, makes respective particulate filters have much better water resistance than those particulate filters having a layer of material A or B (i.e., inorganic particles of irregular shape) . On the other hand, the particulate filters having a layer of inorganic particles of material C does not exhibit satisfied water resistance yet.
[0318] Surprisingly, the particulate filters having a layer of inorganic particles of material D retained a rather high level of FFE between 89%to 99%after water treatment, which is desirable for the application in treating exhaust from a gasoline engine.
[0319] Particularly, it can be seen from the comparison between the particulate filters having a layer of material C and the particulate filters having a layer of inorganic particles of material D, the inorganic particles of plate-like crystals having the required anti-agglomeration index significantly improve the water resistance of the particulate filters.
[0320] III. 2 Particulate Filters with In-wall TWC Coating (FWC)
[0321] Reference Example 2-1 (R2-1)
[0322] A particulate filter having a TWC coating was used as a reference filter, which was prepared from a blank filter substrate which has a size of 132.1 mm (D) × 101.6 mm (L) , a volume of 1.4 L (about 85.4 in3) , a cell density of 300 cells per square inch (cpsi) , a wall thickness of 8 mils, a porosity of 65%as determined by a mercury intrusion measurement, by applying a TWC washcoat into both inlet channels and outlet channels of the blank filter.
[0323] 15.25 g of 9.68 wt%aqueous rhodium nitrate solution was impregnated in a planetary mixer (P-mixer) onto 640 g of a high surface area gamma alumina powder to form a wet powder while achieving incipient wetness. 30.17 g of 16.31 wt%aqueous hexahydroxy platinic acid diethanolamine salt solution was impregnated in planetary mixer (P-mixer) onto 1785 g of a ceria / zirconia (40%ceria) composite powder to form a wet powder while achieving incipient wetness. An aqueous slurry was formed by mixing above two wet powders with 2590 g of D. I. water, to which 196 g of barium nitrate and 170 g of 21.6 wt%aqueous zirconium nitrate solution were added. The pH of the slurry was adjusted to 3.6 with nitric acid. The slurry was milled to a particle size D90 of 4.5 μm, and then coated into the inlet channels of the blank filter with 50%of the washcoat loading and into the outlet channels of the blank filter with the rest 50%of the washcoat loading. Then, the coated substrate was dried at a temperature of 150 ℃ for 1 hour and then calcined at a temperature of 550 ℃ for 1 h.
[0324] The in-wall TWC coating was obtained with a washcoat loading of about 1.47 g / in3 (90 g / L) and a total PGM loading of about 6.5 g / ft3 (0.23 g / L) with a Pt / Rh ratio of 5 / 1.5.
[0325] Reference Example 2-2 (R2-1)
[0326] A particulate filter having a TWC coating after water treatment was provided.
[0327] A particulate filter having a TWC coating which is same as Reference Example 2-1 was placed horizontally in water at a depth of 2 cm for 10 minutes. Then, the filter was dried at a temperature of 200 ℃ for 4 hours.
[0328] Comparative Example 2-1 (C2-1)
[0329] A particulate filter having a TWC coating and a layer of inorganic particles of material A was prepared.
[0330] A particulate filter having a TWC coating was firstly prepared by applying the same process as described in Reference Example 2-1. Then, A powder of material A was mixed with a carrier gas and blown into the inlet channels of the filter at a flow rate of 600 m3 / h at room temperature. The loading of the material A was 1 g / L (0.016 g / in3) .
[0331] Comparative Example 2-2 (C2-2)
[0332] A particulate filter having a TWC coating and a layer of inorganic particles of material A after water treatment was provided.
[0333] A particulate filter which is same as Comparative Example 2-1 was subjected to the same water treatment as described in Reference Example 2-2.
[0334] Comparative Example 2-3 (C2-3)
[0335] A particulate filter having a TWC coating and a layer of inorganic particles of material A was prepared.
[0336] A particulate filter was prepared by the same process as in Comparative Example 2-1, except that the loading of the material A was 3 g / L (0.049 g / in3) .
[0337] Comparative Example 2-4 (C2-4)
[0338] A particulate filter having a TWC coating and a layer of inorganic particles of material A after water treatment was provided.
[0339] A particulate filter which is same as Comparative Example 2-3 was subjected to the same water treatment as described in Reference Example 2-2.
[0340] Comparative Example 2-5 (C2-5)
[0341] A particulate filter having a TWC coating and a layer of inorganic particles of material A was prepared.
[0342] A particulate filter was prepared by the same process as in Comparative Example 2-1, except that the loading of the material A was 5 g / L (0.082 g / in3) .
[0343] Comparative Example 2-6 (C2-6)
[0344] A particulate filter having a TWC coating and a layer of inorganic particles of material A after water treatment was provided.
[0345] A particulate filter which is same as Comparative Example 2-5 was subjected to the same water treatment as described in Reference Example 2-2.
[0346] Comparative Example 2-7 (C2-7)
[0347] A particulate filter having a TWC coating and a layer of inorganic particles of material B was prepared.
[0348] A particulate filter having a TWC coating was firstly prepared by applying the same process as described in Reference Example 2-1. Then, a powder of material B was mixed with a carrier gas and blown into the inlet channels of the filter at a flow rate of 600 m3 / h at room temperature. The loading of the material B was 1 g / L (0.016 g / in3) .
[0349] Comparative Example 2-8 (C2-8)
[0350] A particulate filter having a TWC coating and a layer of inorganic particles of material B after water treatment was provided.
[0351] A particulate filter which is same as Comparative Example 2-7 was subjected to the same water treatment as described in Reference Example 2-2.
[0352] Comparative Example 2-9 (C2-9)
[0353] A particulate filter having a TWC coating and a layer of inorganic particles of material B was prepared.
[0354] A particulate filter was prepared by the same process as in Comparative Example 2-7, except that the loading of the material B was 3 g / L (0.049 g / in3) .
[0355] Comparative Example 2-10 (C2-10)
[0356] A particulate filter having a TWC coating and a layer of inorganic particles of material B after water treatment was provided.
[0357] A particulate filter which is same as Comparative Example 2-9 was subjected to the same water treatment as described in Reference Example 2-2.
[0358] Comparative Example 2-11 (C2-11)
[0359] A particulate filter having a TWC coating and a layer of inorganic particles of material B was prepared.
[0360] A particulate filter was prepared by the same process as in Comparative Example 2-7, except that the loading of the material B was 5 g / L (0.082 g / in3) .
[0361] Comparative Example 2-12 (C2-12)
[0362] A particulate filter having a TWC coating and a layer of inorganic particles of material B after water treatment was provided.
[0363] A particulate filter which is same as Comparative Example 2-11 was subjected to the same water treatment as described in Reference Example 2-2.
[0364] Inventive Example 2-1 (E2-1)
[0365] A particulate filter having a TWC coating and a layer of inorganic particles of material D was prepared.
[0366] A particulate filter having a TWC coating was firstly prepared by applying the same process as described in Reference Example 2-1. Then, a powder of material D was mixed with a carrier gas and blown into the inlet channels of the filter at a flow rate of 600 m3 / h at room temperature. The loading of the material D was 10 g / L (0.164 g / in3) .
[0367] Inventive Example 2-2 (E2-2)
[0368] A particulate filter having a TWC coating and a layer of inorganic particles of material D after water treatment was provided.
[0369] A particulate filter which is same as Inventive Example 2-1 was subjected to the same water treatment as described in Reference Example 2-2.
[0370] Inventive Example 2-3 (E2-3)
[0371] A particulate filter having a TWC coating and a layer of inorganic particles of material D was prepared.
[0372] A particulate filter was prepared by the same process as in Inventive Example 2-1, except that the loading of the material D was 20 g / L (0.328 g / in3) .
[0373] Inventive Example 2-4 (E2-4)
[0374] A particulate filter having a TWC coating and a layer of inorganic particles of material D after water treatment was provided.
[0375] A particulate filter which is same as Inventive Example 2-3 was subjected to the same water treatment as described in Reference Example 2-2.
[0376] Inventive Example 2-5 (E2-5)
[0377] A particulate filter having a TWC coating and a layer of inorganic particles of material D was prepared.
[0378] A particulate filter was prepared by the same process as in Inventive Example 2-1, except that the loading of the material D was 30 g / L (0.492 g / in3) .
[0379] Inventive Example 2-6 (E2-6)
[0380] A particulate filter having a TWC coating and a layer of inorganic particles of material D after water treatment was provided.
[0381] A particulate filter which is same as Inventive Example 2-5 was subjected to the same water treatment as described in Reference Example 2-2.
[0382] Inventive Example 2-7 (E2-7)
[0383] A particulate filter having a TWC coating and a layer of inorganic particles of material D was prepared.
[0384] A particulate filter was prepared by the same process as in Inventive Example 2-1, except that the loading of the material D was 50 g / L (0.819 g / in3) .
[0385] Inventive Example 2-8 (E2-8)
[0386] A particulate filter having a TWC coating and a layer of inorganic particles of material D after water treatment was provided.
[0387] A particulate filter which is same as Inventive Example 2-7 was subjected to the same water treatment as described in Reference Example 2-2.
[0388] The particulate filters comprising an in-wall TWC coating (FWCs) as prepared in above Examples were tested for the Filtration Performance with respect to the back pressure (BP) and the fresh filtration efficiency (FFE) in accordance with the methods as described hereinabove. The test results for the particulate filters are summarized in Table 3 below.
[0389] Table 3
[0390] Group 2-I
[0391] This group includes FWCs R2-1, C2-1, C2-3, C2-5, C2-7, C2-9 and C2-11, E2-1, E2-3, E2-5 and E2-7 respectively. The backpressure (BP) and fresh filtration efficiency (FFE) of those particulate filters are shown in Figs. 7 and 8 respectively.
[0392] It can be seen from the comparison of the FWCs having a layer of inorganic particles with the FWC R2-1 without a layer of inorganic particles, the fresh filtration efficiency (FFE) can be improved by applying a layer of inorganic particles onto the porous walls of the inlet channels of the substrate with an acceptably Iow increase of back pressure. The FFE of those FWCs having a layer of organic particles ranges from 70%to 97%.
[0393] Group 2-II
[0394] This group includes FWCs R2-2, C2-2, C2-4, C2-6, C2-8, C2-10 and C2-12, E2-2, E2-4, E2-6 and E2-8, which correspond to the particulate filters of Group 2-I respectively but have been subjected to water treatment. The backpressure (BP) and fresh filtration efficiency (FFE) of this group of particulate filters are also shown in Figs. 7 and 8, respectively.
[0395] The influences of different inorganic particles on the water resistance of the particulate filters can determined from the comparison between corresponding particulate filters of group 2-I and group 2-II.
[0396] The FWCs having a layer of inorganic particles of material A or B all exhibited significant decrease of FFE after water treatment. The FFE of those FWCs decreases to a level between 54%and 64%. Those particulate filters did not exhibit acceptable water resistance, and the FFE improvement resulted from applying a layer of inorganic particles materially lost due to water treatment.
[0397] Surprisingly, the particulate filters having a layer of inorganic particles of material D retained a rather high level of FFE between 70%to 93%after water treatment. The inorganic particles of plate-like crystals having the required anti-agglomeration index also improve the water resistance of the particulate filters comprising an in-wall TWC. In other words, the benefits of a layer of inorganic particles of plate-like crystals having the required anti-agglomeration index to the water resistance of particulate filters were also achieved in the presence of an in-wall TWC coating (i.e., FWC) .
[0398] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those of skill in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the appended claims and their equivalents.
Claims
1.A particulate filter, which comprises-a substrate, comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,-a layer of inorganic particles loaded on surfaces of porous walls in the inlet channels and / or outlet channels, which comprises inorganic particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,in whichM represents the anti-agglomeration index,W1 represents initial weight of the sample,W2 represents weight of dispersed inorganic particles,P1 represents initial particle size D50 of the sample, andP2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,and-optionally, an in-wall TWC coating in the inlet channels and / or outlet channels.2.The particulate filter according to claim 1, which does not comprise the in-wall TWC coating.3.The particulate filter according to claim 1, which comprises the in-wall TWC coating in the inlet channels and / or outlet channels.4.The particulate filter according to any of preceding claims, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index of at least 70%, more preferably 80%, most preferably 90%, in water.5.The particulate filter according to any of preceding claims, wherein the layer of inorganic particles substantially consists of the inorganic particles of plate-like crystals.6.The particulate filter according to any of preceding claims, wherein the inorganic particles, particularly the inorganic particles of plate-like crystals, are particles of a non-PGM inorganic material, particularly selected from alumina, hydrated alumina, boehmite, zirconia, ceria, silica, titania, magnesium oxide, zinc oxide, zinc carbonate, calcium oxide, calcium carbonate, silicate zeolite, aluminosilicate zeolite, or any combinations thereof.7.The particulate filter according to claim 6, wherein the non-PGM inorganic material is selected from alumina, hydrated alumina, boehmite, silica, zinc oxide, zirconia, or any combinations thereof, preferably alumina, boehmite or a combination thereof.8.The particulate filter according to any of preceding claims, wherein the plate-like crystals have an average crystal diameter of no more than 20 μm, no more than 10 μm, no more than 5 μm, or no more than 3 μm, as measured by a scanning electron microscope (SEM) .9.The particulate filter according to any of preceding claims, wherein the plate-like crystals have an average crystal thickness of no more than 1000 nm, no more than 500 nm, or no more than 300 nm, as measured by a scanning electron microscope (SEM) .10.The particulate filter according to any of preceding claims, wherein the plate-like crystals have an aspect ratio of at least 3, for example at least 5, and no more than 100, for example no more than 50, no more than 30, no more than 20, or no more than 15.11.The particulate filter according to any of preceding claims, which comprises the layer of inorganic particles at a loading of from 1 to 500 g / L or from 2 to 300 g / L.12.The particulate filter according to any of preceding claims 1, 2 and 4 to 10, which comprises the layer of inorganic particles at a loading of from 1 to 200 g / L, from 2 to 100 g / L, from 3 to 50 g / L, or from 10 to 40 g / L.13.The particulate filter according to any of preceding claims 1 and 3 to 10, which comprises the layer of inorganic particles at a loading of from 1 to 500 g / L, from 2 to 200 g / L, from 5 to 100 g / L, or from 10 to 60 g / L.14.The particulate filter according to any of preceding claims, wherein the in-wall TWC coating is in form of a washcoat comprising a TWC composition, preferably comprising a rhodium component and a platinum component which are supported on support particles selected from refractory metal oxides, oxygen storage components and any combinations thereof, more preferably being free or substantially free of a palladium component.15.The particulate filter according to any of preceding claims, which is a gasoline particulate filter.16.A method for producing a particulate filter as defined in any of claims 1 to 15, which includes-providing a substrate comprising a plurality of porous walls extending longitudinally to form a plurality of parallel channels extending from an inlet end to an outlet end, wherein a quantity of the channels are inlet channels that are open at the inlet end and closed at the outlet end, and a quantity of channels are outlet channels that are closed at the inlet end and open at the outlet end,-optionally, applying a TWC coating in the porous walls in the inlet and / or outlet channels of the substrate,-applying inorganic particles or precursors thereof on surfaces of porous walls in the inlet channels and / or outlet channels, wherein at least part of the inorganic particles or precursors thereof are particles of plate-like crystals, wherein the inorganic particles of plate-like crystals have an anti-agglomeration index (M) of at least 50%in water, as determined by subjecting a sample of the inorganic particles of plate-like crystals to dispersing in water, separating and collecting dispersed inorganic particles and undispersed inorganic particles, and calculating in accordance with the following equation,in whichM represents the anti-agglomeration index,W1 represents initial weight of the sample,W2 represents weight of dispersed inorganic particles,P1 represents initial particle size D50 of the sample, andP2 represents particle size D50 of a mixture of the dispersed inorganic particles and the undispersed inorganic particles after collecting and drying,and-optionally, drying and / or calcining.17.The method according to claim 16, wherein the inorganic particles are applied by a dry coating or washcoating process, preferably by a dry coating process.18.The method according to claim 16 or 17, wherein the in-wall TWC coating is applied before applying the inorganic particles on surfaces of the porous walls.19.An exhaust treatment system, which comprises a particulate filter according to any of claims 1 to 15 or a particulate filter obtainable or obtained from the method according to any of claims 16 to 18, and is located downstream of a gasoline engine.20.A method for treating an exhaust stream from a gasoline engine, which includes contacting the exhaust stream with a particulate filter according to any of claims 1 to 15, a particulate filter obtainable or obtained from the method according to any of claims 16 to 18, or an exhaust treatment system as defined in claim 19.
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