EXHAUST GAS-PURIFYING CATALYST

Abstract

An exhaust gas-purifying catalyst includes a catalyst-coated filter. The catalyst-coated filter includes a filter substrate and a catalyst layer on a pore wall of the filter substrate. The exhaust gas-purifying catalyst has a first end, a second end, a porous wall, a first cell, and a second cell. The first cell is closed at the second end, the second cell is closed at the first end, and the first cell and the second cell are adjacent to each other with the porous wall interposed therebetween. At a surface of the porous wall on the first cell side, a proportion S.sub.S/S of a total area S.sub.S of pores having an opening diameter of less than 40 μm in a total area S of all pores is 65% or more.

Claims

1. An exhaust gas-purifying catalyst comprising a catalyst-coated filter, the catalyst-coated filter comprising a filter substrate and a catalyst layer on a pore wall of the filter substrate, wherein the exhaust gas-purifying catalyst has a first end, a second end, a porous wall, a first cell, and a second cell, the first cell extending from the first end toward the second end, being opened at the first end, and being closed at the second end, the second cell extending from the second end toward the first end, being opened at the second end, and being closed at the first end, and the first cell and the second cell being adjacent to each other with the porous wall interposed therebetween, and the porous wall has a proportion S.sub.S/S of 65% or more at a surface on the first cell side, the proportion S.sub.S/S being a proportion of a total area S.sub.S of pores having an opening diameter of less than 40 μm at the surface in a total area S of all pores at the surface.

2. The exhaust gas-purifying catalyst according to claim 1, wherein the porous wall has a proportion S.sub.M/S of 30% or less at the surface, the proportion S.sub.M/S being a proportion of a total area S.sub.M of pores having an opening diameter of 40 μm or more and less than 60 μm at the surface in the total area S of all the pores.

3. The exhaust gas-purifying catalyst according to claim 1, wherein the porous wall has a proportion S.sub.L/S of 15% or less at the surface, the proportion S.sub.L/S being a proportion of a total area S.sub.L of pores having an opening diameter of 60 μm or more at the surface in the total area S of all the pores.

4. The exhaust gas-purifying catalyst according to claim 1, wherein the porous wall has a proportion S.sub.SS/S of 50% or less at the surface, the proportion S.sub.SS/S being a proportion of a total area S.sub.SS of pores having an opening diameter of less than 20 μm at the surface in the total area S of all the pores.

5. The exhaust gas-purifying catalyst according to claim 1, wherein a portion of the porous wall on the first cell side has a cross section perpendicular to the surface, pores of the filter substrate include first pores having a pore diameter of 5 μm or more and less than 10 μm at the cross section, second pores having a pore diameter of 10 μm or more and less than 20 μm at the cross section, and third pores having a pore diameter of 20 μm or more at the cross section, a filling rate R.sub.F1 of the first pores with the catalyst layer, a filling rate R.sub.F2 of the second pores with the catalyst layer, and a filling rate R.sub.F3 of the third pores with the catalyst layer satisfy a relationship represented by an inequality R.sub.F1<R.sub.F2<R.sub.F3.

6. The exhaust gas-purifying catalyst according to claim 5, wherein the filling rate R.sub.F1 is 40% or less, the filling rate R.sub.F2 is 40% or less, and the filling rate R.sub.F3 is 45% or less.

7. The exhaust gas-purifying catalyst according to claim 5, wherein the filling rate R.sub.F3 is 20% or more.

8. The exhaust gas-purifying catalyst according to claim 1, wherein a ratio of a mass of the catalyst layer to a volume of the filter substrate is in a range of 10 g/L to 300 g/L.

9. The exhaust gas-purifying catalyst according to claim 1, further comprising inorganic particles in a powder form supported by the catalyst-coated filter.

10. The exhaust gas-purifying catalyst according to claim 9, wherein the inorganic particles are localized on the first cell side of the porous wall.

11. The exhaust gas-purifying catalyst according to claim 9, wherein an amount A, an amount A1, and an amount A2 satisfy a relationship represented by an inequality (A1+A2)/A≥90%, the amount A being a total amount of the inorganic particles, the amount A1 being an amount of the inorganic particles positioned above a surface of the catalyst-coated filter on the first cell side, and the amount A2 being an amount of the inorganic particles which are in pores of the catalyst-coated filter and whose distances from the surface of the catalyst-coated filter on the first cell side is 20% or less of a thickness of a portion of the catalyst-coated filter corresponding to the porous wall.

12. The exhaust gas-purifying catalyst according to claim 9, wherein the pores of the porous wall include first small pores having an opening diameter of less than 40 μm at the surface and first large pores having an opening diameter of 40 μm or more at the surface, and pores of a portion of the catalyst-coated filter corresponding to the porous wall include second small pores having an opening diameter of less than 40 μm at a surface of the portion on the first cell side and second large pores having an opening diameter of 40 μm or more at the surface of the portion, a ratio (S.sub.S2−S.sub.S1)/S.sub.S2 of a difference S.sub.S2−S.sub.S1 between a total area S.sub.S2 of the second small pores and a total area S.sub.S1 of the first small pores to the total area S.sub.S2 of the second small pores is 40% or less, and a ratio (S.sub.L2−S.sub.L1)/S.sub.L2 of a difference S.sub.L2−S.sub.L1 between a total area S.sub.L2 of the second large pores and a total area S.sub.L1 of the first large pores to the total area S.sub.L2 of the second large pores is 60% or more.

13. The exhaust gas-purifying catalyst according to claim 9, wherein the inorganic particles have an average particle size in a range of 1 μm to 50 μm.

14. The exhaust gas-purifying catalyst according to claim 9, wherein the inorganic particles comprise one or more selected from the group consisting of a metal oxide, a metal hydroxide, a metal carbonate, a metal phosphate, a metal nitrate, a metal sulfate, and a clay mineral.

15. The exhaust gas-purifying catalyst according to claim 9, wherein a ratio of a mass of the inorganic particles to a volume of the filter substrate is in a range of 3 g/L to 50 g/L.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0095] FIG. 1 is a schematic cross-sectional view of an exhaust gas-purifying catalyst according to an embodiment of the present invention.

[0096] FIG. 2 is an enlarged cross-sectional view of a porous wall of the exhaust gas-purifying catalyst shown in FIG. 1.

[0097] FIG. 3 is a further enlarged cross-sectional view of the porous wall of the exhaust gas-purifying catalyst shown in FIG. 1.

[0098] FIG. 4 is a cross-sectional view showing a method of separating connected pores in a cross-sectional image of the porous wall.

[0099] FIG. 5 is a schematic plan view of a first cell-side surface of the porous wall.

[0100] FIG. 6 is an image obtained by binarizing a micrograph of a porous wall of an exhaust gas-purifying catalyst according to Example 1.

[0101] FIG. 7 is an image obtained by binarizing a micrograph of a porous wall of an exhaust gas-purifying catalyst according to Comparative Example 1.

[0102] FIG. 8 is a graph showing a distribution of the opening diameters obtained for the porous walls of the exhaust gas-purifying catalysts according to Example 1 and Comparative Examples 1 to 3.

[0103] FIG. 9 is a graph showing a distribution of powder-form inorganic particles in the thickness direction obtained for the porous wall of the exhaust gas-purifying catalyst according to Example 1.

[0104] FIG. 10 is a graph showing a relationship between the proportion S.sub.s/S and the pressure loss after PM accumulation obtained for the porous walls of the exhaust gas-purifying catalysts according to Example 1 and Comparative Examples 1 to 3.

[0105] FIG. 11 is a graph showing a distribution of the opening diameters obtained for the porous walls of the exhaust gas-purifying catalysts according to Examples 1 to 4.

[0106] FIG. 12 is a graph showing a distribution of the opening diameters obtained for the porous walls of the exhaust gas-purifying catalysts according to Examples 1 and 5 and Comparative Examples 1 and 5.

DETAILED DESCRIPTION

[0107] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The embodiments described below further embody any one of the above aspects.

[0108] Each of the features described below can be combined with each of the aspects described above. Also, a combination of two or more of the features described below can be combined with each of the aspects described above.

[0109] In the drawings referred to below, elements having the same or similar functions are denoted by the same reference symbols, and repeat descriptions will be omitted. The dimensional ratio and the shape shown in the respective drawings may be different from the actual ones.

[0110] FIG. 1 is a schematic cross-sectional view of an exhaust gas-purifying catalyst according to an embodiment of the present invention. FIG. 2 is an enlarged cross-sectional view of a porous wall of the exhaust gas-purifying catalyst shown in FIG. 1. FIG. 3 is a further enlarged cross-sectional view of the porous wall of the exhaust gas-purifying catalyst shown in FIG. 1. In FIGS. 1 and 2, the outlined arrow indicates a flow direction of exhaust gas.

[0111] An exhaust gas-purifying catalyst 1 shown in FIGS. 1 to 3 is a particulate filter including a catalyst layer 22 shown in FIGS. 2 and 3. The exhaust gas-purifying catalyst 1 has a substantially columnar shape. As shown in FIG. 1, the exhaust gas-purifying catalyst 1 includes a first end E1, a second end E2, porous walls W, first cells C1, and second cells C2. The first end E1 and the second end E2 are bases of the column.

[0112] The first cells C1 extend from the first end E1 toward the second end E2. The first cells C1 are opened at the first end E1 and closed at the second end E2.

[0113] The second cells C2 extend from the second end E2 toward the first end E1. The second cells C2 are opened at the second end E2 and closed at the first end E1.

[0114] The first cell C1 and the second cell C2 are adjacent to each other with the porous wall W interposed therebetween. The first cells C1 and the second cells C2 are arranged to form a checkered pattern at the first end E1 and the second end E2.

[0115] The exhaust gas-purifying catalyst 1 includes a catalyst-coated filter 2, as shown in FIGS. 1 to 3. The catalyst-coated filter 2 includes a filter substrate 21 and a catalyst layer 22, as shown in FIGS. 2 and 3.

[0116] The filter substrate 21 includes a honeycomb structure 211 and plugs 212a and 212b, as shown in FIG. 1.

[0117] The honeycomb structure 211 is a column provided with through-holes each extending from one of the bases to the other of the bases. One of the bases corresponds to the first end E1, and the other of the bases corresponds to the second end E2. The honeycomb structure 211 includes walls 211W forming side walls of the through-holes. The walls 211W are porous and separate the adjacent through-holes.

[0118] The plugs 212a block some of the holes of the honeycomb structure 211 on the second end E2 side. The first cells C1 are positioned in spaces each surrounded by the plug 212a blocking the hole on the second end E2 side and the wall 211W forming the sidewall of the hole.

[0119] The plugs 212b block the remaining holes of the honeycomb structure 211 on the first end E1 side. The second cells C2 are positioned in spaces each surrounded by the plug 212b blocking the hole on the first end E1 side and the wall 211W forming the sidewall of the hole.

[0120] These plugs 212a and 212b are disposed in such a manner that the hole whose second end E2 side is blocked by the plug 212a and the hole whose first end E1 side is blocked by the plug 212b are adjacent to each other with the wall 211W interposed therebetween. The first cell C1 and the second cell C2 are adjacent to each other in such a manner that the wall 211W of the filter substrate 21 and the catalyst layer 22 provided on the pore walls of the filter substrate 21 are interposed between the first cell C1 and the second cell C2.

[0121] The catalyst layer 22 is supported by the filter substrate 21, as shown in FIGS. 2 and 3. Specifically, the catalyst layer 22 is provided on the pore walls of the filter substrate 21. Namely, the catalyst layer 22 covers the pore inner walls of the wall 211W.

[0122] In this structure, the catalyst layer 22 is provided over the entire thickness of the porous wall W or the wall 211W. A portion of the catalyst layer 22 which covers the pore inner walls of the wall 211W and whose distance from the surface of the wall 211W on the first cell C1 side is equal to or greater than a predetermined value can be omitted. Namely, the entire catalyst layer 22 may be positioned on the portion of the porous wall W or the wall 211W on the first cell C1 side.

[0123] The wall 211W and the portion of the catalyst layer 22 supported by the wall 211W form the filter wall 21W. The filter wall 21W is porous.

[0124] The exhaust gas-purifying catalyst 1 further includes inorganic particles 3, as shown in FIGS. 2 and 3. The inorganic particles 3 are positioned on the surface of the porous wall W or the filter wall 21W on the first cell C1 side or positioned near said surface.

[0125] The inorganic particles 3 are in a powder form. Although at least some of the inorganic particles 3 are adhered to the catalyst-coated filter 2, the inorganic particles 3 are not fixed to the catalyst-coated filter 2. Also, the inorganic particles 3 are not fixed to each other. The inorganic particles 3 can be fixed by heat treatment or chemical treatment.

[0126] The inorganic particles 3 reduce the pore diameter of the pores near the surface of the porous wall W on the first cell C1 side. Near the surface of the porous wall W on the first cell C1 side, the filling rate of the pores of the filter wall 21W with the inorganic particles 3 tends to be low for the pores having a small opening diameter and tends to be high for the pores having a large opening diameter.

[0127] In the exhaust gas-purifying catalyst 1, a proportion S.sub.S/S of a total area S.sub.S of the pores having an opening diameter of less than 40 μm at the surface of the porous wall W on the first cell C1 side in a total area S of all the pores at the surface is 65% or more. As described above, in such an exhaust gas-purifying catalyst 1, PM is less likely to reach the pores positioned far away from the surface of the porous wall W on the first cell C1 side. Therefore, the amount of PM accumulated in the pores P of the porous wall W is small, and narrowing or closure of a gas passage in the porous wall W is less likely to occur. Accordingly, the pressure loss of the exhaust gas-purifying catalyst 1 caused by accumulation of PM is small.

[0128] The catalyst layer 22 is preferably configured so that the porous wall W has the structure described below.

[0129] Namely, it is preferable that the portion of the porous wall W on the first cell C1 side has a cross section perpendicular to the surface of the porous wall W on the first cell C1 side, the pores of the filter substrate 21 include first pores having a pore diameter of 5 μm or more and less than 10 μm at the cross section, second pores having a pore diameter of 10 μm or more and less than 20 μm at the cross section, and third pores having a pore diameter of 20 μm or more at the cross section, and a ratio R.sub.F1 of a total area S.sub.C1 of the portions of the catalyst layer 22 positioned in the first pores to a total area S.sub.F1 of the first pores, a ratio R.sub.F2 of a total area S.sub.C2 of the portions of the catalyst layer 22 positioned in the second pores to a total area S.sub.F2 of the second pores, and a ratio R.sub.F3 of a total area S.sub.C3 of the portions of the catalyst layer 22 positioned in the third pores to a total area S.sub.F3 of the third pores satisfy a relationship represented by the inequality R.sub.F1<R.sub.F2<R.sub.F3. Herein, the boundary between the pores connected to each other and the pore diameter of the respective pores are determined by the method described later with reference to FIG. 4.

[0130] In such a configuration, for example, the portion of the filter wall 21W near the surface on the first cell C1 side has a width of the pore size distribution narrower and an average pore diameter smaller than those of the portion of the wall 211W near the surface on the first cell C1 side.

[0131] FIG. 4 is a cross-sectional view showing a method of separating connected pores in a cross-sectional image of the porous wall. FIG. 4 corresponds to a cross-sectional image of the porous wall W. In FIG. 4, the catalyst layer 22 and the inorganic particles 3 described later are omitted.

[0132] (Step S1)

[0133] In this method, firstly, an image of a cross section of the porous wall W is captured using an electron scanning microscope (SEM) or a transmission electron microscope (TEM). This cross section is a cross section perpendicular to the surface of the porous wall W on the first cell C1 side, that is, a cross section parallel to the thickness direction of the porous wall W.

[0134] (Step S2)

[0135] Next, the wall 211W of the filter substrate 21 (hereinafter referred to as a “wall portion”) is specified in the image thus obtained. A space portion is specified in the wall portion. In this step, not only a space portion spaced apart from both surfaces of the wall 211W as shown by a space portion CV1, but also a space portion opened on at least one of the surfaces of the wall 211W as shown by a space portion CV2 are specified. A part of the catalyst layer 22 or inorganic particles 3 may be positioned in the space portion. Then, one of the space portions is selected.

[0136] (Step S3)

[0137] Next, an area of the selected space portion is determined, and a diameter of a circle having the same area as the area of the selected space portion, that is, an equivalent circle diameter is calculated. Then, whether or not the equivalent circle diameter is 5 μm or less is determined.

[0138] (Step S4)

[0139] If the equivalent circle diameter is 5 μm or less, it is determined that the above space portion corresponds to a single pore, and the equivalent circle diameter thereof is set as the pore diameter of this pore. If there are non-selected space portions, one of the non-selected space portions is selected, and the process returns to step S3. If there are no non-selected space portions, the process is completed.

[0140] When the space portion CV1 is selected in the example shown in FIG. 4, it is determined that the space portion CV1 corresponds to a single pore P1 because the equivalent circle diameter of the space portion CV1 is 5 μm or less. This equivalent circle diameter is determined to be the pore diameter of the pore P1. Then, the non-selected space portion CV2 is selected, and the process returns to step S3.

[0141] (Step S5)

[0142] If the equivalent circle diameter is more than 5 μm, it is determined that the above space portion corresponds to two or more pores connected to each other. The space portion is divided at positions where the equivalent circle diameter is reduced to 50% of the equivalent circle diameter of more than 5 μm, and the boundaries between the regions created thereby are determined as boundaries of the pores.

[0143] When the space portion CV2 is selected in the example shown in FIG. 4, it is determined that the space portion CV2 corresponds to two or more pores connected to each other because the equivalent circle diameter of the space portion CV2 is more than 5 μm. The space portion CV2 is divided at positions where the equivalent circle diameter is reduced to 50% of the equivalent circle diameter of more than 5 μm, and the boundaries between the regions created thereby are determined as boundaries of the pores.

[0144] (Substep SS1)

[0145] To be specific, firstly, a number of circles that are inscribed in the space portion are created such that each circle is in contact with a pair of wall surface portions facing each other with the space portion interposed therebetween. Herein, the wall surface portion is a portion corresponding to the boundary between the space portion and the wall portion. In this substep, only the circles whose respective centers are positioned between a pair of main surfaces of the wall 211W are created. A reference line is created by connecting the centers of these circles. In the example shown in FIG. 4, the branched broken line CL is the reference line obtained by connecting the centers of the circles.

[0146] (Substep SS2)

[0147] Next, among the above circles, a circle having the largest diameter is specified (hereinafter, the circle is referred to as a “reference circle”). In the example shown in FIG. 4, the circle IC1 is specified.

[0148] (Substep SS3)

[0149] Subsequently, the diameters of the circles whose centers are aligned in one direction (hereinafter referred to as a “first direction”) from the center of the reference circle along the reference line are confirmed by starting from a circle having a center closest to the center of the reference circle. The confirmation of the diameters is performed until a circle having a diameter which is 50% of the diameter of the reference circle is found.

[0150] When such a circle (hereinafter referred to as a “first circle”) is found, a line segment connecting two contact points between the first circle and the wall surface portions is set as the boundary dividing the space portion. If the first circle is not found, no boundary dividing the space portion is set for the portion of the reference line on the first direction side with respect to the center of the reference circle.

[0151] In the example shown in FIG. 4, when the diameters of the circles whose centers are aligned in a downward direction from the center of the circle IC1 along the broken line CL are confirmed by starting from a circle having a center closest to the center of the circle IC1, a circle IC2 is found as a circle having a diameter which is 50% of the diameter of the circle IC1. Therefore, a line segment B1 connecting two contact points between the circle IC2 and the wall surface portions is set as a boundary dividing the space portion CV2.

[0152] (Substep SS4)

[0153] Subsequently, the diameters of the circles whose centers are aligned in a reverse direction (hereinafter referred to as a “second direction”) from the center of the reference circle along the reference line are confirmed by starting from a circle having a center closest to the center of the reference circle. The confirmation of the diameters is performed until a circle having a diameter which is 50% of the diameter of the reference circle is found.

[0154] When such a circle (hereinafter referred to as a “second circle”) is found, a line segment connecting two contact points between the second circle and the wall surface portions is set as a boundary dividing the space portion. When the second circle is not found, no boundary dividing the space portion is set for the portion of the reference line on the second direction side with respect to the center of the reference circle.

[0155] In the example shown in FIG. 4, even when the diameters of the circles whose centers are aligned in an upward direction from the center of the circle IC1 along the broken line CL are confirmed by starting from a circle having a center closest to the center of the circle IC1, a circle having a diameter which is 50% of the diameter of the circle IC1 is not found. Therefore, no boundary dividing the space portion CV2 is set for the portion of the broken line CL on the upper direction side with respect to the center of the circle IC1.

[0156] (Substep SS5)

[0157] Determination is made as to whether or not the reference line is branched within the range of the portion corresponding to the line connecting the centers of the circles whose diameters were confirmed in substep SS4 or SS5.

[0158] If the reference line is branched within the above range, the same processing as that of substep SS4 is also performed for the respective branch destinations.

[0159] Namely, the diameters of the circles whose centers are aligned in a branched direction (hereinafter referred to as a “third direction”) from the branch point along the reference line are confirmed by starting from a circle having a center closest to the branch point. The confirmation of the diameters is performed until a circle having a diameter which is 50% of the diameter of the reference circle is found.

[0160] When such a circle (hereinafter referred to as a “third circle”) is found, a line segment connecting two contact points between the third circle and the wall surface portions is set as the boundary dividing the space portion. If the third circle is not found, no boundary dividing the space portion is set for the portion of the reference line on the third direction side with respect to the branch point.

[0161] When the above processing is completed, or when the reference line is not branched within the aforementioned range, the process proceeds to next step S6.

[0162] In the example shown in FIG. 4, the broken line CL is not branched within the range of the portion corresponding to the line connecting the centers of the circles whose diameters were confirmed based on the circle IC1 as a reference circle in substep SS4 or SS5. Therefore, the process proceeds to next step S6 without setting an additional boundary in substep SS5.

[0163] (Step S6)

[0164] In step S6, whether or not a boundary has been set in step S5 is determined.

[0165] (Step S7)

[0166] If not a single boundary is set in step S5, it is determined that the above-described space portion is a single pore, and the equivalent circle diameter thereof is set as the pore diameter of this pore. If there are non-selected space portions, one of the non-selected space portions is selected, and the process returns to step S3. If there are no non-selected space portions, the process is completed.

[0167] (Step S8)

[0168] If one or more boundaries are set in step S5, it is determined that a region where the center of the reference circle is positioned among the regions formed by dividing the above-described space portion with a boundary is a single pore, and the equivalent circle diameter thereof is set as the pore diameter of this pore.

[0169] Subsequently, the portion excluding the above region, in which the center of the reference circle is positioned, from the above space portion is set as a new space portion. Selecting this space portion, the process returns to step S3.

[0170] In the example shown in FIG. 4, it is determined that a region where the center of the circle IC1 is positioned among the regions formed by dividing the space portion CV2 with a boundary B1 is a single pore P2, and the equivalent circle diameter thereof is set as the pore diameter of the pore P2. Then, the portion excluding the region corresponding to the pore P2, in which the center of the circle IC1 is positioned, from the space portion CV2 (hereinafter said portion is referred to as a “first remaining portion”) is set as a new space portion. Selecting this space portion, the process returns to step S3.

[0171] Since the above first remaining portion has an equivalent circle diameter of more than 5 μm, a circle IC3 is specified as a reference circle in step S5. No additional reference line may be created. In step S5, circles IC4a and IC4b having a diameter which is 50% of the diameter of the circle IC3 and boundaries B1 and B2 are further specified. Through step S6, it is then determined in step S8 that a region where the center of the circle IC2 is positioned among the regions formed by dividing the first remaining portion with the boundaries B1 and B2 is a single pore P3, and the equivalent circle diameter thereof is set as the pore diameter of the pore P3. Then, the portion excluding the region corresponding to the pore P3, in which the center of the circle IC2 is positioned, from the first remaining portion (hereinafter said portion is referred to as a “second remaining portion”) is set as a new space portion. Selecting this space portion, the process returns to step S3.

[0172] Since the above second remaining portion has an equivalent circle diameter of 5 μm or less, it is determined in step S4 that the second remaining portion corresponds to a single pore P4, and the equivalent circle diameter thereof is set as the pore diameter of the pore P4. If there are non-selected space portions, one of the non-selected space portions is selected, and the process returns to step S3. If there are no non-selected space portions, the process is completed.

[0173] The porous wall W preferably has the structure described below with reference to FIG. 5.

[0174] FIG. 5 is a schematic plan view of the first cell-side surface of the porous wall. FIG. 5 shows the surface of the porous wall W on the first cell C1 side.

[0175] On the aforementioned surface, the pores P of the porous wall W are classified into first small pores having an opening diameter of less than 40 μm and first large pores having an opening diameter of 40 μm or more. For example, in FIG. 5, the pores P on the lower right side and the upper left side are the first large pores, and the remaining pores P are the first small pores. The circle formed by the broken line LL2 is a circle having an area equal to the area of the opening of the pore P. Therefore, the opening diameters of the pores P are the diameters of the circles formed by the broken line LL2.

[0176] On the first cell-side surface of the portion of the catalyst-coated filter corresponding to the porous wall W, that is, the first cell-side surface of the filter wall 21W, the pores of the filter wall 21W are classified into second small pores having an opening diameter of less than 40 μm and second large pores having an opening diameter of 40 μm or more. For example, in FIG. 5, the pores on the lower right side and the upper left side among the pores of the filter wall 21W are the second large pores, and the remaining pores are the second small pores. In FIG. 5, the pores of the filter wall 21W are the regions surrounded by a solid line LL1. Therefore, the opening diameters of the pores of the filter wall 21W are the diameters of the circles having an area equal to the areas of the regions surrounded by the solid line LL1.

[0177] A proportion (S.sub.S2−S.sub.S1)/S.sub.S2 of a difference S.sub.S2−S.sub.S1 between a total area S.sub.S2 of the second small pores and a total area S.sub.S1 of the first small pores to the total area S.sub.S2 of the second small pores is 40% or less. Also, a proportion (S.sub.L2−S.sub.L1)/S.sub.L2 of a difference S.sub.L2−S.sub.L1 between a total area S.sub.L2 of the second large pores and a total area S.sub.L1 of the first large pores to the total area S.sub.L2 of the second large pores is 60% or more.

[0178] In the above structure, the degree of reduction of the opening diameters of the second large pores due to application of inorganic particles 3 is larger than that of the second small pores. Such a configuration is advantageous for, for example, reducing the number of pores P having an excessively large opening diameter or an excessively small opening diameter on the first cell-side surface of the porous wall.

EXAMPLES

[0179] Specific examples of the present invention will be described below.

[0180] <1> Production of Exhaust Gas-Purifying Catalyst

Example 1

[0181] The exhaust gas-purifying catalyst described with reference to FIGS. 1 to 3 was produced by the method described below.

[0182] First, a solution of palladium nitrate in an amount of 3 parts by mass, an alumina powder in an amount of 35 parts by mass, a ceria-containing oxide in an amount of 32 parts by mass, and ion-exchanged water were mixed together. A polycarboxylic acid in an amount of 1 part by mass was mixed in the resultant mixed solution, thereby preparing a slurry. The slurry had a viscosity η.sub.400 of 100 mPa.Math.s at a temperature of 25° C. and a shear rate of 400 s.sup.−1.

[0183] Next, a filter substrate was prepared. In this example, a columnar filter substrate having a volume of 1.3 L and a height of 114.3 mm was used.

[0184] Next, the above slurry was supplied to one of the end surfaces (a first end surface) of the filter substrate, and gas in the filter substrate was suctioned from the other of the end surfaces (a second end surface) of the filter substrate. The suctioning was performed at a temperature of 25° C. and under the conditions where a linear velocity (wind velocity) of gas flow near an end of the filter substrate when the filter substrate was installed and there was no supply of the slurry was 50 m/s. In this manner, the wall of the filter substrate was coated with the slurry. The slurry was supplied so that the amount of a catalyst layer with respect to the volume of the filter substrate was 75 g/L in the catalyst-coated filter.

[0185] Then, the filter substrate coated with the slurry was dried and calcined.

[0186] In this manner, the catalyst-coated filter was obtained.

[0187] Next, inorganic particles were supplied to one of the surfaces of each filter wall of the catalyst-coated filter. Specifically, aerosol containing inorganic particles as aerosol particles was supplied to the first end portion of the catalyst-coated filter corresponding to the first end surface. Along with this, gas in the catalyst-coated filter was suctioned from the second end portion of the catalyst-coated filter corresponding to the second end surface. The suctioning was performed with the catalyst-coated filter arranged so that the first end portion thereof faces downward.

[0188] The amount of the inorganic particles with respect to the volume of the filter substrate was 5 g/L. As the inorganic particles, sepiolite, which is a porous inorganic substance, having an average particle size of 6 μm was used.

[0189] In this manner, an exhaust gas-purifying catalyst was obtained.

Comparative Example 1

[0190] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that supply of inorganic particles to the catalyst-coated filter was omitted. Namely, a catalyst-coated filter was produced by the same method as described in Example 1 and used as the exhaust gas-purifying catalyst according to Comparative Example 1.

Comparative Example 2

[0191] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that the proportion of the amount of the catalyst layer to the volume of the filter substrate was changed from 75 g/L to 50 g/L and supply of inorganic particles to the catalyst-coated filter was omitted.

Comparative Example 3

[0192] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that the proportion of the amount of the catalyst layer to the volume of the filter substrate was changed from 75 g/L to 100 g/L and supply of inorganic particles to the catalyst-coated filter was omitted.

[0193] <2> Measurement of Opening Diameter

[0194] The opening diameters on the first cell-side surface of the porous wall of the respective exhaust gas-purifying catalysts according to Example 1 and Comparative Examples 1 to 3 were measured by the above-described method. The results are shown in FIGS. 6 to 8 and Table 1.

TABLE-US-00001 Amount (g/L) Catalyst Inorganic S.sub.<20/S S.sub.20-40/S S.sub.40-60/S S.sub.60-80/S S.sub.80-100/S S.sub.100</S layer particles (%) (%) (%) (%) (%) (%) Ex. 1 75 5 43.4 38.4 13.6 4.6 0 0 Comp. 75 0 28.1 31.7 21.6 9.6 5.6 3.5 Ex. 1 Comp. 50 0 24.9 35.3 21.7 13 2.8 2.1 Ex. 2 Comp. 100 0 28.1 28.3 22.4 9.9 6.6 4.7 Ex. 3

[0195] FIG. 6 is an image obtained by binarizing a micrograph of the porous wall of the exhaust gas-purifying catalyst according to Example 1. FIG. 7 is an image obtained by binarizing a micrograph of the porous wall of the exhaust gas-purifying catalyst according to Comparative Example 1. FIG. 8 is a graph showing a distribution of the opening diameters obtained for the porous walls of the exhaust gas-purifying catalysts according to Example 1 and Comparative Examples 1 to 3.

[0196] In Table 1, “S.sub.<20/S” represents a proportion of a total area S.sub.<20 of pores having an opening diameter of less than 20 μm in the total area S of all the pores in the micrograph of the first cell-side surface of the porous wall. “S.sub.20-40/S” represents a proportion of a total area S.sub.20-40 of pores having an opening diameter in a range of 20 μm or more and less than 40 μm in the total area S of all the pores in the above micrograph. “S.sub.40-60/S” represents a proportion of a total area S.sub.40-60 of pores having an opening diameter in a range of 40 μm or more and less than 60 μm in the total area S of all the pores in the above micrograph. “S.sub.60-80/S” represents a proportion of a total area S.sub.60-80 of pores having an opening diameter in a range of 60 μm or more and less than 80 μm in the total area S of all the pores in the above micrograph. “S.sub.80-100/S” represents a proportion of a total area S.sub.80-100 of pores having an opening diameter in a range of 80 μm or more and less than 100 μm in the total area S of all the pores in the above micrograph. “S.sub.100</S” represents a proportion of a total area S.sub.100< of pores having an opening diameter of 100 μm or more in the total area S of all the pores in the above micrograph.

[0197] As shown in FIGS. 6 to 8 and Table 1, in the exhaust gas-purifying catalyst according to Example 1, a proportion of pores having a large opening diameter on the first cell-side surface of the porous wall was smaller than that in the exhaust gas-purifying catalyst according to Comparative Examples 1 to 3.

[0198] <3> Measurement of Filling Rate

[0199] For the exhaust gas-purifying catalyst according to Example 1, the above-described proportion (S.sub.S2−S.sub.S1)/S.sub.S2 and proportion (S.sub.L2−S.sub.L1)/S.sub.L2 were calculated.

[0200] Specifically, for the exhaust gas-purifying catalyst according to Example 1, a sum of the total areas S.sub.<20 and S.sub.20-40 obtained for calculating the above opening diameter was determined as the total area S.sub.S1 of the exhaust gas-purifying catalyst according to Example 1. Also, for the exhaust gas-purifying catalyst according to Example 1, a sum of the total areas S.sub.40-60, S.sub.60-80, S.sub.80-100, and S.sub.100< obtained for calculating the above opening diameter was determined as the total area S.sub.L1 of the exhaust gas-purifying catalyst according to Example 1. For the exhaust gas-purifying catalyst according to Comparative Example 1, a sum of the total areas S.sub.<20 and S.sub.20-40 obtained for calculating the above opening diameter was determined as the total area S.sub.S2 of the exhaust gas-purifying catalyst according to Comparative Example 1. Also, for the exhaust gas-purifying catalyst according to Comparative Example 1, a sum of the total areas S.sub.40-60, S.sub.60-80, S.sub.80-100, and S.sub.100< obtained for calculating the above opening diameter was determined as the total area S.sub.L2 of the exhaust gas-purifying catalyst according to Comparative Example 1. The results of the calculation are shown in Table 2 below.

TABLE-US-00002 S.sub.S1 S.sub.S2 S.sub.L1 S.sub.L2 (S.sub.S2 − S.sub.S1)/S.sub.S2 (S.sub.L2 − S.sub.L1)/S.sub.L2 Ex. 1 55103 40043 37079 8938 0.273 0.759

[0201] As shown in Table 2, in the exhaust gas-purifying catalyst according to Example 1, the proportion (S.sub.L2−S.sub.L1)/S.sub.L2 was larger than the proportion (S.sub.S2−S.sub.S1)/S.sub.S2. Namely, in the exhaust gas-purifying catalyst according to Example 1, the pores having a large opening diameter among the pores opened on the first cell-side surface of the porous wall had a higher filling rate with the inorganic particles than that of the pores having a small opening diameter.

[0202] <4> Measurement of Distribution of Inorganic Particles

[0203] A distribution of the inorganic particles in the thickness direction of the porous wall of the exhaust gas-purifying catalyst according to Example 1 was measured. Specifically, an image of a cross section of the porous wall of the exhaust gas-purifying catalyst according to Example 1 was captured by an electron scanning microscope to obtain a gray-scale image. The imaging was performed on the cross section of the portion of the porous wall where a distance from the first end is equal to a distance from the second end. Next, the position of analysis by an energy dispersive X-ray analyzer was specified on the obtained gray-scale image to measure the intensity of the character X-rays originating in calcium. Herein, a linear analysis along the thickness direction of the porous wall was performed. A composite image formed by superimposing points that are colored and have a brightness (gray value) corresponding to the intensity of the character X-rays on the obtained gray-scale image was generated. A relationship between the distance from the first cell-side surface of the catalyst-coated filter and the gray value was determined from the composite image.

[0204] FIG. 9 is a graph showing a distribution of powdered inorganic particles in the thickness direction obtained for the porous wall of the exhaust gas-purifying catalyst according to Example 1. In FIG. 9, the horizontal axis represents a distance from the first cell-side surface of the catalyst-coated filter, and the vertical axis represents the above gray value.

[0205] As shown in FIG. 9, in the exhaust gas-purifying catalyst according to Example 1, the inorganic particles were localized on the first cell side of the porous wall. In the exhaust gas-purifying catalyst according to Example 1, the above-described amounts A, A1, and A2 satisfied the relationship represented by the inequality (A1+A2)/A≥90%. Specifically, the proportion (A1+A2)/A was 98.7%.

[0206] <5> Evaluation of Pressure Loss

[0207] The pressure loss of the respective exhaust gas-purifying catalysts according to Example 1 and Comparative Examples 1 to 3 was evaluated. Specifically, light oil was burned using a soot generator to generate PM, and PM was accumulated in the respective exhaust gas-purifying catalysts. At the point of time when the amount of PM accumulated reached 1 g/L, the pressure loss of the respective exhaust gas-purifying catalysts was measured. The pressure loss was measured at a gas temperature of 240° C. and a gas flow rate of 250 kg/hour. The results are shown in Table 3 and FIG. 10.

TABLE-US-00003 TABLE 3 Amount (g/L) Pressure Catalyst Inorganic S.sub.S/S S.sub.M+L/S loss layer particles (%) (%) (mbar) Ex. 1 75 5 81.8 18.2 42.5 Comp. 75 0 59.8 40.2 56.5 Ex. 1 Comp. 50 0 60.3 39.7 54.1 Ex. 2 Comp. 100 0 56.4 43.6 65.3 Ex. 3

[0208] In FIG. 10, the horizontal axis represents the above proportion S.sub.s/S, and the vertical axis represents the pressure loss. In Table 3 and FIG. 10, the proportion S.sub.S/S is a sum of the above proportions S.sub.<20/S and S.sub.20-40/S. Also, in Table 3, the proportion S.sub.M+L/S is a sum of the above proportions S.sub.40-60/S, S.sub.60-80/S, S.sub.80-100/S, and S.sub.100</S.

[0209] As shown in Table 3 and FIG. 10, the proportion S.sub.s/S of the exhaust gas-purifying catalyst according to Example 1 was larger than that of the exhaust gas-purifying catalysts according to Comparative Examples 1 to 3, and the pressure loss of the exhaust gas-purifying catalyst according to Example 1 after PM accumulation was smaller than that of the exhaust gas-purifying catalysts according to Comparative Examples 1 to 3.

[0210] <6> Production of Exhaust Gas-Purifying Catalyst

Example 2

[0211] An exhaust gas-purifying catalyst was produced by the same method as described Example 1, except that the ratio of the amount of the catalyst layer to the volume of the filter substrate was changed from 75 g/L to 50 g/L.

Example 3

[0212] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that the ratio of the amount of the catalyst layer to the volume of the filter substrate was changed from 75 g/L to 100 g/L.

Example 4

[0213] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that the ratio of the amount of the catalyst layer to the volume of the filter substrate was changed from 75 g/L to 125 g/L.

Example 5

[0214] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that the amount of the inorganic particles with respect to the volume of the filter substrate was changed from 5 g/L to 20 g/L.

Comparative Example 4

[0215] An exhaust gas-purifying catalyst was produced by the same method as described in Example 1, except that the amount of the inorganic particles with respect to the volume of the filter substrate was changed from 5 g/L to 1 g/L.

[0216] <7> Influence of Amount of Catalyst Layer on Opening Diameter

[0217] The opening diameters on the first cell-side surface of the porous wall of the exhaust gas-purifying catalysts according to Examples 2 to 4 were measured by the same method as described above. The results are shown in Table 4 and FIG. 11.

TABLE-US-00004 Amount (g/L) Catalyst Inorganic S.sub.<20/S S.sub.20-40/S S.sub.40-60/S S.sub.60-80/S S.sub.80-100/S S.sub.100</S layer particles (%) (%) (%) (%) (%) (%) Ex. 1 75 5 43.4 38.4 13.6 4.6 0 0 Ex. 2 50 5 43.5 34 15.5 7 0 0 Ex. 3 100 5 44.9 35.5 14.6 5 0 0 Ex. 4 125 5 42.4 35.4 17 5.2 0 0

[0218] As shown in Table 4, when the amount of the catalyst layer was sufficiently large, the proportion of the pores having a large opening diameter on the first cell-side surface of the porous wall was successfully reduced by producing an exhaust gas-purifying catalyst by the above-described method. However, when the amount of the catalyst layer was increased, the total area S of all the pores was decreased. Specifically, the total areas S of all the pores obtained in the exhaust gas-purifying catalysts according to Examples 2, 3, and 4 were respectively over 1.3 times, over 0.7 times, and less than 0.4 times the total area S of all the pores obtained in the exhaust gas-purifying catalyst according to Example 1.

[0219] <8> Influence of Amount of Inorganic Particles on Opening Diameter

[0220] The opening diameters on the first cell-side surface of the porous wall of the exhaust gas-purifying catalysts according to Example 5 and Comparative Example 4 were measured by the same method as described above. The results are shown in Table 5 and FIG. 12.

TABLE-US-00005 Amount (g/L) Catalyst Inorganic S.sub.<20/S S.sub.20-40/S S.sub.40-60/S S.sub.60-80/S S.sub.80-100/S S.sub.100</S layer particles (%) (%) (%) (%) (%) (%) Ex. 1 75 5 43.4 38.4 13.6 4.6 0 0 Ex. 5 5 20 91.9 8.1 0 0 0 0 Comp. 75 0 28.1 31.7 21.6 9.6 5.6 3.5 Ex. 1 Comp. 75 1 38.7 29.2 14.4 7 3.6 7 Ex. 4

[0221] As shown in Table 5, when the amount of the inorganic particles was increased, the proportion of the pores having a large opening diameter on the first cell-side surface of the porous wall was decreased.

[0222] <9> Measurement of Filling Rate

[0223] The filling rates R.sub.F1, R.sub.F2, and R.sub.F3 of the exhaust gas-purifying catalysts according to Examples 1 to 5 and Comparative Examples 1 to 4 were obtained by the method described with reference to FIG. 4. As an example, the result obtained for the exhaust gas-purifying catalyst according to Example 3 is shown in Table 6 below.

TABLE-US-00006 TABLE 6 R.sub.F1 (%) R.sub.F2 (%) R.sub.F3 (%) Ex. 3 30.7 33.8 43.1

[0224] In all of the exhaust gas-purifying catalysts according to Examples 1 to 5 and Comparative Examples 1 to 4, the filling rates R.sub.F1, R.sub.F2, and R.sub.F3 satisfied the relationship represented by the inequality R.sub.F1<R.sub.F2<R.sub.F3, the filling rate R.sub.F1 was in the range of 10% to 40%, the filling rate R.sub.F2 was in the range of 15% to 40%, and the filling rate R.sub.F3 was in the range of 20% to 45%.

REFERENCE SIGNS LIST

[0225] 1. Exhaust gas-purifying catalyst [0226] 2. Catalyst-coated filter [0227] 3. Inorganic particle [0228] 21. Filter substrate [0229] 21W. Filter wall [0230] 22. Catalyst layer [0231] 211. Honeycomb structure [0232] 211W. Wall [0233] 212a. Plug [0234] 212b. Plug [0235] B1. Boundary [0236] B2. Boundary [0237] C1. First cell [0238] C2. Second cell [0239] CV1. Space portion [0240] CV2. Space portion [0241] CL. Broken line [0242] E1. First end [0243] E2. Second end [0244] IC1. Circle [0245] IC2. Circle [0246] IC3. Circle [0247] IC4a. Circle [0248] IC4b. Circle [0249] P1. Pore [0250] P2. Pore [0251] P4. Pore [0252] W. Porous wall