Embodiments of the present disclosure generally relate to catalytically active particulate filters, in particular catalytically active particulate filter bodies with high filtration efficiency, and methods of manufacture thereof.
Particulate filters, for example, diesel particulate filters and gasoline particulate filters (GPFs), filter particulates from the exhaust stream from engines such as automotive vehicles burning diesel and gasoline fuel, respectively. In various engine exhaust configurations, a catalytically active particulate filter may provide a reduced space requirement and/or increased catalytic performance for exhaust flows.
In a first aspect, a method is disclosed herein for making a catalyzed particulate filter with high clean filtration efficiency and low pressure drop. In some embodiments, the method comprises applying a catalyst material to a filter body comprising porous filter walls and filtration material comprised of filtration particles disposed on or in or both on and in the porous filter walls, and the filtration material is hydrophobic while the catalyst material is applied to the filter body. In some embodiments, the methods disclosed herein are advantageous to making a filter body with predominantly or mostly in-wall catalyst loading, preferably with little infiltration, and more preferably no infiltration, of catalyst material among the filtration particles.
In a second aspect, a catalyzed particulate filter with high clean filtration efficiency is disclosed herein, wherein the filter comprises porous filter walls comprising filtration particles disposed on or in or both on and in the porous filter walls, and catalyst material disposed on or in or both on and in the porous filter walls, and wherein the catalyst material substantially is not present among the filtration particles. In some embodiments, the filter body is advantageously provided with predominantly or mostly in-wall catalyst loading, preferably with little to no infiltration of catalyst material among the filtration particles.
Additional embodiments of the disclosure are disclosed herein.
So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.
Before describing several exemplary embodiments of the disclosure, it is to be understood that the disclosure is not limited to the details of construction or process steps set forth in the following description. The disclosure is capable of other embodiments and of being practiced or being carried out in various ways. As used herein, “volume of filter body” or “liter of filter body” refers to the overall volume as calculated by the overall axial length of the filter body multiplied by the area of an end (such as the inlet end) of the filter body (pi/4 times square of outside diameter). As used herein, “filter matrix volume” is equal to the closed frontal area of a honeycomb matrix structure multiplied by the axial length of the honeycomb structure for an unplugged honeycomb structure, such that the closed frontal area is the area occupied by the various honeycomb matrix walls at the inlet end of the honeycomb structure. Also as used herein, “predominantly in-wall” or “mostly in-wall” catalyst loading of a porous wall such as a porous wall of a honeycomb structure refers to the catalyst material being disposed within the porous wall and an on-wall catalyst material thickness of 0 to 25 micrometers thickness at any location on the surface of the wall; thus, a honeycomb structure or matrix comprised of porous walls, like porous ceramic walls, which comprises a “predominantly in-wall” or “mostly in-wall” catalyst loading, may have one or more wall surfaces upon which a 25 micrometer thickness or less of catalyst material, or no catalyst material, is disposed on the surfaces of the walls of the honeycomb matrix, or “on-wall”. Preferably for embodiments disclosed herein, there is no on-wall component of catalyst material disposed on gas inlet surfaces of matrix wall surfaces; in some embodiments, there is also no on-wall component of catalyst material (on-wall catalyst material thickness of 0 micrometers) disposed on some, and more preferably all, gas outlet surfaces of matrix wall surfaces, e.g. on second wall surfaces defining outlet channels.
In one set of embodiments, a method is disclosed herein of making a porous ceramic honeycomb filter body, the method comprising: depositing filtration material comprising filtration particles onto porous filter walls of a filter structure, wherein the filter structure comprises a matrix of the filter walls configured as a cellular honeycomb structure comprised of cells wherein surfaces of the filter walls define channels comprising inlet channels and outlet channels extending from an inlet end to an outlet end of the filter structure, wherein the filter structure comprises a first group of plugs disposed within and sealing the inlet channels at or near the outlet end and a second group of plugs disposed within and sealing the outlet channels at or near the inlet end, wherein the porous filter walls comprise opposing first and second wall surfaces and the filtration particles are supported by the filter walls on, in, or both on and in, the first wall surfaces, then, heat treating the filter structure to provide filtration material heat treatment by heating the filter structure to one or more filtration heat treatment temperatures less than or equal to 500° C. and for a time sufficient to reduce hydrophobicity of the filtration material, wherein the filtration material is hydrophobic prior to the depositing and/or hydrophobicity is imparted to the filtration material after the depositing and prior to the heat treating, and depositing catalytic material onto the second surfaces of the porous filter walls, such that the catalytic material is disposed in the filter walls and/or on the second surfaces of the filter walls, wherein the second surfaces define the outlet channels.
In some embodiments, the filtration material exhibits hydrophobicity prior to the depositing.
In some embodiments, the filtration material exhibits hydrophobicity prior to the heat treating.
In some embodiments, a mixture of the filtration particles and a carrier gas are transported through a duct toward the filter body lodged at a downstream end of the duct and into an inlet end of the filter body. In some of these embodiments, the filtration material comprises filtration particles and one or more hydrophobic organic materials. In some of these embodiments, at least one hydrophobic organic material and the filtration particles are mixed prior to being mixed with the carrier gas. In some of these embodiments, the organic material and filtration particles are injected from a nozzle into the carrier gas.
In some embodiments, at least some of the hydrophobicity of the filtration material remains after the filtration material heat treatment.
In some embodiments, the filter structure is heat treated to provide filtration material heat treatment for greater than 0.5 hours and less than 10 hours.
In some embodiments, the method further comprises reducing the hydrophobicity of the filtration material after the catalytic material is deposited.
In some embodiments, the method further comprises eliminating the hydrophobicity of the filtration material after the catalytic material is deposited.
In some embodiments, the method further comprises heat treating the filter structure after the depositing of the catalytic material.
In some embodiments, the method further comprises heat treating the filter structure after the depositing of the catalytic material for a time and at one or more temperatures sufficient to calcine the catalytic material.
In some embodiments, the depositing catalytic material comprises depositing successive loads of catalytic material. In some of these embodiments, the filter structure is heated between the loadings of catalytic material without removing the hydrophobicity of the filtration material.
In some embodiments, the depositing catalytic material comprises depositing successive loadings of catalytic material, wherein the catalytic material is dried between the loadings of catalytic material.
In some embodiments, the method further comprises heat treating the filter structure after a selected amount of catalytic material has been deposited by heating the filter structure to a heat treatment temperature of greater than 500° C. for greater than 1 hour.
In some embodiments, a selected amount of catalytic material is deposited, and wherein the resulting catalyst loading is between 1 and 500 g/liter catalytic material per volume of filter structure.
In some embodiments, the depositing of the catalytic material comprises applying a catalyst material slurry to the second surfaces of the filter walls.
In some embodiments, the filtration material is comprised of inorganic filtration particles and binder material. In some of these embodiments, the binder material exhibits hydrophobicity; in some embodiments, the binder material comprises a silicon containing material; in some embodiments, the binder material comprises a silicone material; in some embodiments, the binder material comprises a silicone resin; in some embodiments, the binder material comprises a siloxane or polysiloxane; in some embodiments, the binder material comprises an alkali siloxane; in some embodiments, the binder material comprises an alkoxysiloxane.
In some embodiments, the filtration particles comprise inorganic nanoparticles; in some embodiments, the inorganic nanoparticles comprise refractory nanoparticles; in some of these embodiments, the refractory nanoparticles are comprised of alumina, aluminum titanate, cordierite, silicon carbide, mullite, spinel, silica, zeolite, zirconia, silicon nitride, zirconium phosphate, or combinations thereof.
In some embodiments, the filtration material comprises agglomerates comprised of inorganic nanoparticles and a binder material which exhibits hydrophobicity.
In some embodiments, the filtration particles are not hydrophobic, and hydrophobicity is imparted to the filtration material prior to the depositing of the catalytic material.
In some embodiments, the filtration particles are not hydrophobic, and hydrophobicity is imparted to the filtration material by mixing the filtration particles with a hydrophobic material prior to the depositing of the catalytic material. In some of these embodiments, the hydrophobic material comprises a hydrophobic organic material.
In another set of embodiments, a method is disclosed herein of making a porous ceramic honeycomb filter body comprising: depositing filtration material comprising filtration particles onto porous filter walls of a filter structure, wherein the filtration material is disposed on or in the filter walls and the filtration material is hydrophobic, and wherein the filter structure comprises a matrix of the filter walls configured as a cellular honeycomb structure comprised of cells wherein surfaces of the filter walls define channels comprising inlet channels and outlet channels extending from an inlet end to an outlet end of the filter structure, wherein the filter structure comprises a first group of plugs disposed within and sealing the inlet channels at or near the outlet end and a second group of plugs disposed within and sealing the outlet channels at or near the inlet end, wherein the porous filter walls comprise opposing first and second wall surfaces and the filtration material is supported by the filter walls on, in, or both on and in, the first wall surfaces, then, heat treating the filter structure to provide filtration material heat treatment by heating the filter structure to one or more filtration heat treatment temperatures and preserving at least some hydrophobicity of the filtration particles, then, depositing catalytic material onto the second surfaces of the porous filter walls, such that the catalytic material is disposed in the filter walls and/or on the second surfaces of the filter walls while the filtration material is hydrophobic, wherein the second surfaces define the outlet channels.
In another set of embodiments, a filter body is disclosed herein comprising a porous honeycomb structure comprised of porous filter walls, filtration particles supported by the porous filter walls, and catalytic material, wherein the structure comprises a matrix of the filter walls having an average wall thickness WT (in mils) and configured as a cellular honeycomb structure comprised of cells having a cell density of CD (cells per square inch), wherein surfaces of the filter walls define channels comprising inlet channels and outlet channels extending from an inlet end to an outlet end of the filter structure, wherein the filter body has an effective diameter D (in inches) and a length L (in inches) extending in an axial direction from the inlet end to the outlet end, wherein the filter structure comprises a first group of plugs disposed within and sealing the inlet channels at or near the outlet end and a second group of plugs disposed within and sealing the outlet channels at or near the inlet end, wherein the porous filter walls comprise opposing first and second wall surfaces, and wherein the filtration particles are disposed in the filter walls and/or on the filter walls at or near the first wall surfaces, wherein the catalytic material is disposed in the porous filter walls and/or on the second surfaces of the porous filter walls, and the catalyst material has a bulk density (BD) in (g/m3 of filter matrix volume), wherein the catalyst loading is disposed predominantly in-wall within the filter walls, wherein the second surfaces define the outlet channels, and wherein the filter body has a clean filtration efficiency at 0.0 particulate loading of greater than 80% normalized to a reference filter body having a reference cell density of 300 cells per square inch and a reference average wall thickness of 8 mils.
In some embodiments, the filter body has a normalized clean filtration efficiency of greater than 85% at 0.0 particulate loading.
In some embodiments, the filter body has a normalized clean filtration efficiency of greater than 90% at 0.0 particulate loading.
In some embodiments, the filter body has a catalyst loading of 150 to 200 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 92%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 2.81 kPa.
In some embodiments, the filter body has a catalyst loading of 200 to 350 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 3.24 kPa.
In some embodiments, the filter body has a catalyst loading of 350 to 580 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 85%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 3.60 kPa.
In some embodiments, the walls of the matrix are configured to define 300 cells per square inch in an axial cross section of the honeycomb structure; the filter walls have an average thickness of 8 mils (203 micrometers); the filter body has a catalyst loading of greater than 350 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 85%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 3.24 kPa.
In some embodiments, the filter body has a catalyst loading of 150 to 200 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 94%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 2.6 kPa.
In some embodiments, the filter body has a catalyst loading of 200 to 350 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 90%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 3.02 kPa.
In some embodiments, the filter body has a catalyst loading of 350 to 580 g/L of catalyst material per filter matrix volume, the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and the filter body exhibits a normalized clean pressure drop at 0.0 g/L of less than 3.40 kPa.
In some embodiments, the walls of the matrix are configured to define 300 cells per square inch in an axial cross section of the honeycomb structure; the filter walls have an average thickness of 8 mils (203 micrometers); the filter body has a catalyst loading of greater than 350 g/L of catalyst material per filter matrix volume, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and the filter body exhibits a clean pressure drop at 0.0 g/L of less than 3.0 kPa.
In some embodiments, the catalytic material is present at a catalyst loading of 40 to 50 g/L of filter body, wherein the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 92%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 115% of its normalized pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of 150 to 200 g/L of filter matrix volume, wherein the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 92%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 115% of its normalized pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of 200 to 350 g/L of filter matrix volume, wherein the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 120% of its normalized pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of 350 to 580 g/L of filter matrix volume, wherein the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 85%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 125% of its normalized pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of greater than 350 g/L of filter matrix volume, wherein the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 85%, and wherein the filter body exhibits a pressure drop at 0.5 g/L particulate loading which is less than 125% of its pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of 150 to 200 g/L of filter matrix volume, wherein the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 94%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 110% of its normalized pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of 200 to 350 g/L of filter matrix volume, wherein the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 90%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 115% of its normalized pressure drop at 0.0 g/L particulate loading.
In some embodiments, the catalytic material is present at a catalyst loading of 350 to 580 g/L of filter matrix volume, wherein the filter body exhibits a normalized clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and wherein the filter body exhibits a normalized pressure drop at 0.5 g/L particulate loading which is less than 120% of its normalized pressure drop at 0.0 g/L particulate loading.
In another set of embodiments, a method is disclosed herein of making a filter body, such as a porous ceramic honeycomb filter body, the method comprising: depositing filtration material onto porous filter walls of a filter structure, wherein the filtration material exhibits hydrophobicity, and wherein the filter structure comprises a matrix of the filter walls configured as a cellular structure, such as a honeycomb structure, comprised of cells wherein surfaces of the filter walls define channels comprising inlet channels and outlet channels, wherein the inlet and outlet channels are thus configured to accommodate flow of a fluid such as an exhaust gas stream carrying particulates into some of the channels and fluid flow out of some of the channels, the channels extending from an inlet end to an outlet end of the filter structure, wherein the filter structure comprises a first group of plugs disposed within and sealing the inlet channels at or near the outlet end and a second group of plugs disposed within and sealing the outlet channels at or near the inlet end, wherein the porous filter walls comprise opposing first and second wall surfaces and the filtration particles are supported by the filter walls in the filter walls and/or on the wall surfaces, for example at or near or proximate the first wall surfaces, then heat treating the filter structure to provide filtration material heat treatment by heating the filter structure to one or more filtration heat treatment temperatures less than 500° C., in some embodiments between 200° C. and 500° C., in some embodiments between 300° C. and 500° C., in some embodiments between 350 and 400° C., for example for 0.1 to 3.0 hours, or 0.1 to 2.0 hours, or 0.5 to 1.5 hours; in some embodiments the temperatures are between 450 and 500° C. for 0.1 to 2.0 hours, in some embodiments the temperatures are between 475 and 495° C. for 0.1 to 0.3 hours, in a manner which preferably tends to preserve or maintain at least some hydrophobicity of the filtration material; then depositing catalytic material onto the second surfaces of the porous filter walls, such that the catalytic material is disposed in the filter walls and/or on the second surfaces of the filter walls, wherein the second surfaces define the outlet channels.
In some embodiments, the hydrophobicity, or at least some of the hydrophobicity, of the filtration material remains after the filtration material heat treatment.
In some embodiments, the filter structure is heat treated to provide filtration material heat treatment for less than 10 hours, and in some embodiments 0.1 to 5 hours, in some embodiments 0.1 to 4 hours, in some embodiments 0.1 to 3 hours, in some embodiments 0.1 to 2 hours, in some embodiments 0.1 to 1.5 hours, and in some embodiments 0.5 to 1.5 hours, such as approximately 1 hour.
The method further preferably comprises reducing the hydrophobicity of the filtration material after the catalytic material is deposited. In some embodiments, the method comprises reducing, removing or essentially eliminating the hydrophobicity of the filtration material after the catalytic material is deposited. In some embodiments, the reduction in hydrophobicity comprises heat treating the filter structure after the depositing of the catalytic material; in some embodiments the method comprises heat treating the filter structure after the depositing of the catalytic material until the hydrophobicity of the filtration material is reduced; in some embodiments, the method comprises heat treating the filter structure after the depositing of the catalytic material until the hydrophobicity of the filtration material is reduced or preferably removed.
In some embodiments, the method further comprises heat treating the filter structure after the depositing of the catalytic material for a time and at one or more temperatures sufficient to calcine the catalytic material.
In some embodiments, the depositing catalytic material comprises depositing successive loads of catalytic material onto the filter body. In some embodiments, the depositing catalytic material comprises depositing successive loadings of catalytic material, wherein the filter structure is heated between the loadings of catalytic material. In some embodiments, the depositing catalytic material comprises depositing successive loadings of catalytic material, wherein the filter structure is heated between the loadings of catalytic material without removing, or without substantially reducing the hydrophobicity of the filtration material; in some of these embodiments, the heating of the filter structure reduces hydrophobicity of the wall itself without substantially affecting the hydrophobicity of the filtration material. In some embodiments, the depositing catalytic material comprises depositing successive loadings of catalytic material, wherein the catalytic material is dried between the loadings of catalytic material. In some embodiments, the depositing catalytic material comprises depositing successive loadings of catalytic material, wherein the catalytic material is dried between the loadings of catalytic material without removing or without substantially reducing the hydrophobicity of the filtration material.
In some embodiments, the depositing catalytic material comprises depositing successive loadings of catalytic material, and in some of these embodiments, the filter structure is heat treated between the loadings of catalytic material.
In some embodiments wherein the method comprises a plurality of loadings of catalytic material, the method further comprises between the loadings of catalytic material the filter structure is heated to a drying temperature which does not exceed 200° C., and in some embodiments does not exceed 150° C., and in some embodiments does not exceed 120° C., and in some embodiments does not exceed 110° C., and in some embodiments does not exceed 100° C. in some embodiments, the filter structure is exposed to a heated environment having a drying temperature which does not exceed 200° C., and in some embodiments does not exceed 150° C., and in some embodiments does not exceed 120° C., and in some embodiments does not exceed 110° C., and in some embodiments does not exceed 100° C.
In some embodiments, the method further comprises heat treating the filter structure after a selected amount of catalytic material has been deposited.
In some embodiments, the method further comprises heat treating the filter structure after a selected amount of catalytic material has been deposited by heating the filter structure to a heat treatment temperature of greater than 300° C., in some embodiments greater than 400° C., in some embodiments greater than 500° C., in some embodiments from 500° C. to 800° C., in some embodiments from 500° C. to 700° C., and in some embodiments from 500° C. to 600° C.
In some embodiments the heat treating reduces the hydrophobicity of the filter particles compared to the hydrophobicity of the filter particles prior to the drying of the catalytic material; in some embodiments, the heat treating reduces the hydrophobicity of the filter particles compared to the hydrophobicity of the filter particles prior to the drying step; in some embodiments, the heat treating reduces the hydrophobicity of the filter particles compared to the hydrophobicity of the filter particles during the depositing of the catalytic material.
In some embodiments, the method further comprises heat treating the filter structure after a selected amount of catalytic material has been deposited by heating the filter structure to a heat treatment temperature of greater than 500° C., in some embodiments greater than 600° C., in some embodiments greater than 700° C., for greater than 1 hour, in some embodiments greater than 2 hours, in some embodiments greater than 3 hours, in some embodiments greater than 4 hours, in some embodiments from 1 to 4 hours, in some embodiments from 1 to 3 hours.
Preferably, a selected amount of catalytic material is deposited. In some embodiments, the selected amount of catalytic material is between 1 and 500 g/liter catalytic material per volume of filter structure.
In some embodiments, the depositing of the catalytic material comprises applying a slurry to the filter structure, the slurry comprising catalytic particles. In some embodiments, the depositing of the catalytic material comprises applying the slurry to the filter walls. In some embodiments, the depositing of the catalytic material comprises applying the slurry to the second surfaces of the filter walls.
In some embodiments, the filtration particles are comprised of inorganic particles and binder material, in some embodiments preferably a hydrophobic binder material. In some embodiments, hydrophobicity can be imparted to the inorganic particles and/or to the binder material, such as after deposition onto the filter part.
In some embodiments, the binder material exhibits hydrophobicity. In some embodiments, the binder material comprises a silicon containing material. In some embodiments, the binder material comprises a silicone material. In some embodiments, the binder material comprises a silicone resin. In some embodiments, the binder material comprises a siloxane or polysiloxane. In some embodiments, the binder material comprises an alkali siloxane. In some embodiments, the binder material comprises an alkoxysiloxane.
In some embodiments, the filtration particles comprise inorganic nanoparticles. In some embodiments, the inorganic nanoparticles comprise refractory nanoparticles. In some embodiments, the refractory nanoparticles are comprised of alumina, aluminum titanate, cordierite, silicon carbide, mullite, spinel, silica, zeolite, zirconia, silicon nitride, zirconium phosphate, and combinations thereof. In some embodiments, the filtration material comprises agglomerates comprised of inorganic nanoparticles, such as agglomerates comprised of inorganic nanoparticles and a binder material which exhibits hydrophobicity. In some embodiments, the filter structure is a honeycomb structure. In some embodiments, the matrix of the filter walls is configured as a honeycomb structure. In some embodiments, the filter body is a porous ceramic honeycomb filter body.
As seen in
Furthermore, there is almost no knee present in the soot loaded pressure drop curve (“SLdP knee”) in embodiments disclosed herein which suggests that a deep bed filtration mechanism which corresponds to higher pressure drop is avoided, and the filtration particles and catalyst material have been processed and are working appropriately. In
where Cup the mass-based filtration where is the upstream concentration as measured by the micro-soot sensor. The corresponding filter soot loading per unit filter volume, SL, at any time, tk, is estimated using the following relation:
where QT is the volumetric flow rate to the filter and Vfilter is the filter volume. As the soot deposits in the filter, the soot itself acts as an additional filtering medium resulting in the increase of filtration efficiency with time. The filtration efficiency gradually increases from clean filter efficiency to steady state efficiency, asymptotically reaching 100% efficiency at higher soot (particulate) loadings.
In some embodiments the filter body disclose herein comprises porous filter walls, or porous wall portions of the filter body which comprise bulk porosity of 40 to 75% as measured by mercury porosimetry.
In some embodiments the porous wall portion comprises walls comprised of cordierite, aluminum titanate, silicon carbide, mullite, spinel, silica, alumina, silicon nitride, and combinations thereof.
In some embodiments the porous wall portion comprises walls arranged in a honeycomb structure of 100 to 900 cells per square inch.
With reference now to
In one or more embodiments, the plugged honeycomb body may be comprised of cordierite, aluminum titanate, enstatite, mullite, forsterite, corundum (SiC), spinel, sapphirine, or periclase, or combinations thereof. In general, cordierite has a composition according to the formula Mg2Al4Si5O18. In some embodiments, the pore size of the ceramic material, the porosity of the ceramic material, and the pore size distribution of the ceramic material are obtained in a controlled manner, for example by varying the particle sizes of the ceramic raw materials. In addition, pore formers can be included in ceramic batches used to form the plugged honeycomb body.
In some embodiments, walls of the plugged honeycomb body may have an average thickness from greater than or equal to 25 μm to less than or equal to 400 μm, such as from greater than or equal to 50 μm to less than or equal to 375 μm, greater than or equal to 75 μm to less than or equal to 350 μm, greater than or equal to 100 μm to less than or equal to 325 μm, greater than or equal to 125 μm to less than or equal to 300 μm, greater than or equal to 150 μm to less than or equal to 300 μm, greater than or equal to 150 μm to less than or equal to 275 μm, greater than or equal to 150 μm to less than or equal to 250 μm, or greater than or equal to 175 μm to less than or equal to 225 μm. The walls of the plugged honeycomb body can be described to have a base portion comprised of a bulk portion (also referred to herein as the bulk), and surface portions (also referred to herein as the surface). The surface portion of the walls extends from a surface of a wall of the plugged honeycomb body into the wall toward the bulk portion of the plugged honeycomb body. The surface portion may extend from 0 (zero) to a depth of about 5 μm into the base portion of the wall of the plugged honeycomb body. In some embodiments, the surface portion may extend about 5 μm, about 7 μm, or about 9 μm (i.e., a depth of 0 (zero)) into the base portion of the wall. The bulk portion of the plugged honeycomb body constitutes the thickness of wall minus the surface portions. Thus, the bulk portion of the plugged honeycomb body may be determined by the following equation: ttotal−2 tsurface where ttotal is the total thickness of the wall and tsurface is the thickness of the wall surface.
In one or more embodiments, the bulk of the plugged honeycomb body (prior to applying any filtration material) has a bulk median pore size from greater than or equal to 7 μm to less than or equal to 25 μm, such as from greater than or equal to 12 μm to less than or equal to 22 μm, or from greater than or equal to 12 μm to less than or equal to 18 μm. For example, in some embodiments, the bulk of the plugged honeycomb body may have bulk median pore sizes of about 10 μm, about 11 μm, about 12 μm, about 13 μm, about 14 μm, about 15 μm, about 16 μm, about 17 μm, about 18 μm, about 19 μm, or about 20 μm. Generally, pore sizes of any given material exist in a statistical distribution. Thus, the term “median pore size” or “d50” (prior to applying any filtration material) refers to a length measurement, above which the pore sizes of 50% of the pores lie and below which the pore sizes of the remaining 50% of the pores lie, based on the statistical distribution of all the pores. Pores in ceramic bodies can be manufactured by at least one of: (1) inorganic batch material particle size and size distributions; (2) furnace/heat treatment firing time and temperature schedules; (3) furnace atmosphere (e.g., low or high oxygen and/or water content), as well as; (4) pore formers, such as, for example, polymers and polymer particles, starches, wood flour, hollow inorganic particles and/or graphite/carbon particles.
In some specific embodiments, the median pore size (d50) of the bulk of the plugged honeycomb body (prior to applying any filtration material) is in a range of from 10 μm to about 16 μm, for example 13-14 μm, and the d10 refers to a length measurement, above which the pore sizes of 90% of the pores lie and below which the pore sizes of the remaining 10% of the pores lie, based on the statistical distribution of all the pores is about 7 μm. In specific embodiments, the d90 refers to a length measurement, above which the pore sizes of 10% of the pores of the bulk of the plugged honeycomb body (prior to applying any filtration material) lie and below which the pore sizes of the remaining 90% of the pores lie, based on the statistical distribution of all the pores is about 30 μm. In specific embodiments, the median diameter (D50) of the secondary particles or agglomerates is about 2 micrometers (μm, or “microns”). In specific embodiments, it has been determined that when the agglomerate median size D50 and the median wall pore size of the bulk honeycomb body d50 is such that there is a ratio of agglomerate median size D50 to median wall pore size of the bulk honeycomb body d50 is in a range of from 5:1 to 16:1, excellent filtration efficiency results and low pressure drop results are achieved. In more specific embodiments, a ratio of agglomerate median size D50 to median wall pore size of the bulk of honeycomb body d50 (prior to applying any filtration material) is in a range of from 6:1 to 16:1, 7:1 to 16:1, 8:1 to 16:1, 9:1 to 16:1, 10:1 to 16:1, 11:1 to 16:1 or 12:1 to 6:1 provide excellent filtration efficiency results and low pressure drop results.
In some embodiments, the bulk of the plugged honeycomb body may have bulk porosities, not counting a coating, of from greater than or equal to 50% to less than or equal to 75% as measured by mercury intrusion porosimetry. Other methods for measuring porosity include scanning electron microscopy (SEM) and X-ray tomography, these two methods in particular are valuable for measuring surface porosity and bulk porosity independent from one another. In one or more embodiments, the bulk porosity of the plugged honeycomb body may be in a range of from about 50% to about 75%, in a range of from about 50% to about 70%, in a range of from about 50% to about 65%, in a range of from about 50% to about 60%, in a range of from about 50% to about 58%, in a range of from about 50% to about 56%, or in a range of from about 50% to about 54%, for example.
In one or more embodiments, the surface portion of the plugged honeycomb body has a surface median pore size from greater than or equal to 7 μm to less than or equal to 20 μm, such as from greater than or equal to 8 μm to less than or equal to 15 μm, or from greater than or equal to 10 μm to less than or equal to 14 μm. For example, in some embodiments, the surface of the plugged honeycomb body may have surface median pore sizes of about 8 μm, about 9 μm, about 10 μm, about 11 μm, about 12 μm, about 13 μm, about 14 μm, or about 15 μm.
In some embodiments, the surface of the plugged honeycomb body may have surface porosities, prior to application of a filtration material deposit, of from greater than or equal to 35% to less than or equal to 75% as measured by mercury intrusion porosimetry, SEM, or X-ray tomography. In one or more embodiments, the surface porosity of the plugged honeycomb body may be less than 65%, such as less than 60%, less than 55%, less than 50%, less than 48%, less than 46%, less than 44%, less than 42%, less than 40%, less than 48%, or less than 36% for example.
Referring now to
In some embodiments described herein, the channel walls 306 of the particulate filter 300 may have a thickness of greater than about 2 mils (50 micrometers, or “microns”), or in some embodiments greater than about 4 mils (101.6 micrometers). For example, in some embodiments, the thickness of the channel walls 306 may be in a range from about 4 mils up to about 30 mils (762 micrometers). In some other embodiments, the thickness of the channel walls 306 may be in a range from about 6 mils (152 micrometers) to about 10 mils (253 micrometers). In some other embodiments, the thickness of the channel walls 206 may be in a range from about 7 mils (177 micrometers) to about 9 mils (228 micrometers).
In some embodiments of the particulate filter 200 described herein the channel walls 306 of the particulate filter 300 may have a bare open porosity (i.e., the porosity before any coating is applied to the plugged honeycomb body) P≥35% prior to the application of any coating to the particulate filter 300. In some embodiments the bare open porosity of the channel walls 306 may be such that 40%≤P 75%. In other embodiments, the bare open porosity of the channel walls 306 may be such that 45%≤P≤75%, 50%≤P≤75%, 55%≤P≤75%, 60%≤P≤75%, 45%≤P≤70%, 50%≤P≤70%, 55%≤P≤70%, or 60%≤P≤70%.
Further, in some embodiments, the channel walls 306 of the particulate filter 300 are formed such that the pore distribution in the channel walls 306 has a median pore size of ≤30 μm (“microns”) prior to the application of any coatings (i.e., bare). For example, in some embodiments, the median pore size may be ≥8 micrometers and less than or ≤30 micrometers. In other embodiments, the median pore size may be ≥10 micrometers and less than or ≤30 micrometers. In other embodiments, the median pore size may be 10 micrometers and less than or ≤25 micrometers. In some embodiments, particulate filters produced with a median pore size greater than about 30 micrometers have reduced filtration efficiency while with particulate filters produced with a median pore size less than about 8 micrometers may be difficult to infiltrate the pores with a washcoat containing a catalyst. Accordingly, in some embodiments, it is desirable to maintain the median pore size of the channel wall in a range of from about 8 micrometers to about 30 micrometers, for example, in a range of from 10 micrometers to about 20 micrometers.
In one or more embodiments described herein, the plugged honeycomb body of the particulate filter 300 is formed from a metal or ceramic material such as, for example, cordierite, silicon carbide, aluminum oxide, aluminum titanate or any other ceramic material suitable for use in elevated temperature particulate filtration applications. For example, the particulate filter 300 may be formed from cordierite by mixing a batch of ceramic precursor materials which may include constituent materials suitable for producing a ceramic article which predominately comprises a cordierite crystalline phase. In general, the constituent materials suitable for cordierite formation include a combination of inorganic components including talc, a silica-forming source, and an alumina-forming source. The batch composition may additionally comprise clay, such as, for example, kaolin clay. The cordierite precursor batch composition may also contain organic components, such as organic pore formers, which are added to the batch mixture to achieve the desired pore size distribution. For example, the batch composition may comprise a starch which is suitable for use as a pore former and/or other processing aids. Alternatively, the constituent materials may comprise one or more cordierite powders suitable for forming a sintered cordierite honeycomb structure upon firing as well as an organic pore former material.
The batch composition may additionally comprise one or more processing aids such as, for example, a binder and a liquid vehicle, such as water or a suitable solvent. The processing aids are added to the batch mixture to plasticize the batch mixture and to generally improve processing, reduce the drying time, reduce cracking upon firing, and/or aid in producing the desired properties in the plugged honeycomb body. For example, the binder can include an organic binder. Suitable organic binders include water soluble cellulose ether binders such as methylcellulose, hydroxypropyl methylcellulose, methylcellulose derivatives, hydroxyethyl acrylate, polyvinylalcohol, and/or any combinations thereof. Incorporation of the organic binder into the plasticized batch composition allows the plasticized batch composition to be readily extruded. In some embodiments, the batch composition may include one or more optional forming or processing aids such as, for example, a lubricant which assists in the extrusion of the plasticized batch mixture. Exemplary lubricants can include tall oil, sodium stearate or other suitable lubricants.
After the batch of ceramic precursor materials is mixed with the appropriate processing aids, the batch of ceramic precursor materials is extruded and dried to form a green honeycomb body comprising an inlet end and an outlet end with a plurality of channel walls extending between the inlet end and the outlet end. Thereafter, the green honeycomb body is fired according to a firing schedule suitable for producing a fired honeycomb body. At least a first set of the channels of the fired honeycomb body can then be plugged in a predefined plugging pattern with a ceramic plugging composition and the honeycomb body is dried and/or heated to secure the plugs in the channels.
In various embodiments the plugged honeycomb body is configured to filter particulate matter from a gas stream, for example, an exhaust gas stream from a gasoline engine. Accordingly, the median pore size, porosity, geometry and other design aspects of both the bulk and the surface of the plugged honeycomb body are selected taking into account these filtration requirements of the plugged honeycomb body. As an example, and as shown in
The filtration particles or filtration material, which in some portions or some embodiments may be an inorganic layer, on walls of the plugged honeycomb body is in some embodiments preferably very thin compared to thickness of the base portion of the walls of the plugged honeycomb body. The material, which may be an inorganic layer, on the plugged honeycomb body can be formed by methods that permit the deposited material to be applied to surfaces of walls of the plugged honeycomb body in very thin applications or in some portions, layers. In embodiments, the average thickness of the material, which may be deposit regions or an inorganic layer, on the base portion of the walls of the plugged honeycomb body is greater than or equal to 0.5 μm and less than or equal to 50 μm, or greater than or equal to 0.5 μm and less than or equal to 45 μm, greater than or equal to 0.5 μm and less than or equal to 40 μm, or greater than or equal to 0.5 μm and less than or equal to 35 μm, or greater than or equal to 0.5 μm and less than or equal to 30 μm, greater than or equal to 0.5 μm and less than or equal to 25 μm, or greater than or equal to 0.5 μm and less than or equal to 20 μm, or greater than or equal to 0.5 μm and less than or equal to 15 μm, greater than or equal to 0.5 μm and less than or equal to 10 μm. In one or more embodiments, the inorganic material comprises alumina.
In another set of embodiments disclosed herein, a filter body is disclosed comprising a porous honeycomb structure comprised of porous filter walls, filtration particles supported by the porous filter walls, and catalytic material, wherein the structure comprises a matrix of the filter walls configured as a cellular honeycomb structure comprised of cells, wherein surfaces of the filter walls define channels comprising inlet channels and outlet channels extending from an inlet end to an outlet end of the filter structure, wherein the filter structure comprises a first group of plugs disposed within and sealing the inlet channels at or near the outlet end and a second group of plugs disposed within and sealing the outlet channels at or near the inlet end, wherein the porous filter walls comprise opposing first and second wall surfaces, and wherein the filtration particles are disposed in the filter walls and/or on the filter walls at or near the first wall surfaces, wherein the catalytic material is disposed in the porous filter walls and/or on the second surfaces of the porous filter walls, wherein the catalyst loading is disposed predominantly in-wall within the filter walls, and wherein the second surfaces define the outlet channels; in some of these embodiments, the filter body has a clean filtration efficiency at 0.0 particulate loading of greater than 80%, the filter body has a catalyst loading of 40 to 50 g/L of catalyst material per volume of filter body, the catalyst loading is disposed predominantly in-wall within the filter walls, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 92%, and the filter body exhibits a ratio of pressure drop at 0.5 g/L soot particulate loading to pressure drop at 0 g/L soot particulate loading of 1.01 to 1.15; in some of these embodiments, the filter body has a catalyst loading of 50 to 90 g/L of catalyst material per volume of filter body, the catalyst loading is disposed predominantly in-wall within the filter walls, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and the filter body exhibits a ratio of pressure drop at 0.5 g/L soot particulate loading to pressure drop at 0 g/L soot particulate loading of 1.01 to 1.20; in some of these embodiments, the filter body has a catalyst loading of 90 to 150 g/L of catalyst material per volume of filter body, the catalyst loading is disposed predominantly in-wall within the filter walls, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 85%, and the filter body exhibits a ratio of pressure drop at 0.5 g/L soot particulate loading to pressure drop at 0 g/L soot particulate loading of 1.01 to 1.25; in some of these embodiments, the filter body has a catalyst loading of 40 to 50 g/L of catalyst material per volume of filter body, the catalyst loading is disposed predominantly in-wall within the filter walls, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 94%, and the filter body exhibits a ratio of pressure drop at 0.5 g/L soot particulate loading to pressure drop at 0 g/L soot particulate loading of 1.01 to 1.10; in some of these embodiments, the filter body has a catalyst loading of 50 to 90 g/L of catalyst material per volume of filter body, the catalyst loading is disposed predominantly in-wall within the filter walls, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 90%, and the filter body exhibits a ratio of pressure drop at 0.5 g/L soot particulate loading to pressure drop at 0 g/L soot particulate loading of 1.01 to 1.15; in some of these embodiments, the filter body has a catalyst loading of 90 to 150 g/L of catalyst material per volume of filter body, the catalyst loading is disposed predominantly in-wall within the filter walls, the filter body exhibits a clean filtration efficiency at 0.0 g/L particulate loading of greater than 88%, and the filter body exhibits a ratio of pressure drop at 0.5 g/L soot particulate loading to pressure drop at 0 g/L soot particulate loading of 1.01 to 1.20.
As described above, the reference filter body performance characteristics are for a filter size of 4.66″ (diameter)×5″ (length), CPSI of 300, web thickness of 8 mil, and TWC bulk density of 1600 g/m3. For filter performance characteristics of filters of other filter geometries, microstructures, and/or catalyst material, the product performance characteristics as claimed herein can be determined by normalization.
As used herein “reference filter body” means a filter body having features of the porous honeycomb structure as present in the target filter body except that the reference filter body has reference geometrical and microstructural features, namely a reference cell density of 300 cells per square inch, a reference average wall thickness of 8 mils, and the reference filter body has a diameter of 4.66″ inches and an axial length of 5 inches, and a catalyst loading bulk density of 1600 g/m3 Thus, for filter bodies which differ from the reference filter body, the filter performance can be normalized to reflect differences in filter size, CPSI, web thickness, and/or catalyst loading per filter matrix volume, in order to evaluate a target filter body with respect to the features and/or performance as claimed in this disclosure.
Thus a comparison evaluation can be made for both FE (filtration efficiency) and dP (pressure drop) performance of filters having different geometries and sizes, as those skilled in the art can normalize results of a target filter body to take into account the impact of size, CPSI and web thickness differences and washcoat density, as appropriate. For such normalization, channel scale 1D FE (SAE 2012-01-0363) and dP (SAE 200-01-0184) models are used for filtration efficiency and pressure drop normalizations, respectively. Normalization for pressure drop of the target filter body is started by selecting an initial estimate of coated wall permeability; the SAE 200-01-0184 dP model is then used with inputs of specific geometry, size and test condition for the target filter body in order to predict pressure drop. If the model predicted pressure drop doesn't match the (“experimentally”) measured value of pressure drop for the target filter body, the difference in those pressure drop values are used to calculate a new estimate of the wall permeability. This iterative process is continued until arriving at a wall permeability value that provides matching of the experimental and modeling results. This equivalent or “extracted” permeability thus provides a good representative value for the actual permeability of the target filter wall. This extracted wall permeability will then be used as input to the model, in combination with the target filter size, geometry and test condition as described in this disclosure (4.66″ diameter×5″ length, CPSI of 300, web thickness of 8 mil) to calculate the pressure drop performance under those conditions. The filtration efficiency (FE) normalization is conducted similarly, however instead of extracting a coated permeability as done for dP, for FE the coated equivalent d50 is extracted and used for the normalization. Thus, those skilled in the art can normalize the catalyst (washcoat) loading if the target filter body comprises a catalyst material with a bulk density different than the reference bulk density described in this disclosure (i.e. bulk density of 1600 g/m3) to arrive at an equivalent catalyst loading (g/L of filter matrix volume) to compare with the described features/performance in the claims of this disclosure.
Reference throughout this specification to “one embodiment,” “certain embodiments,” “one or more embodiments” or “an embodiment” means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.
Although the disclosure herein has been described with reference to particular embodiments, those skilled in the art will understand that the embodiments described are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present disclosure without departing from the spirit and scope of the disclosure. Thus, the present disclosure can include modifications and variations that are within the scope of the appended claims and their equivalents.
This application is a continuation of International Application No. PCT/US2022/012418 filed on Jan. 14, 2022, which claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 63/139,185 filed on Jan. 19, 2021, the content of which is relied upon and incorporated herein by reference in its entirety.
Number | Date | Country | |
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63139185 | Jan 2021 | US |
Number | Date | Country | |
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Parent | PCT/US2022/012418 | Jan 2022 | US |
Child | 18223207 | US |