Patent Application
20240149260
The present application claims priority from Japanese patent application JP 2022-178392 filed on Nov. 7, 2022, the entire content of which is hereby incorporated by reference into this application.
The present disclosure relates to an exhaust gas purification device.
An exhaust gas emitted from an internal combustion engine used in a vehicle, such as an automobile, contains a harmful substance, such as carbon monoxide (CO), hydrocarbon (HC), and nitrogen oxide (NOx). Regulations on emission amounts of these harmful substances have been tightened year by year. To remove these harmful substances, a noble metal, such as platinum (Pt), palladium (Pd), and rhodium (Rh), has been used as a catalyst.
JP 2008-279428 A discloses an exhaust gas purification catalyst that includes a catalyst layer provided with pores. JP 2008-279428 A discloses that the catalyst layer contains a catalyst powder containing a noble metal, and Pd and Rh are exemplified as the noble metal.
JP 2022-061298 A discloses an exhaust gas purification device that includes a substrate and a catalyst layer formed on the substrate. The exhaust gas purification device of JP 2022-061298 A includes a first catalyst layer formed in contact with the substrate over an upstream region in a flow direction of an exhaust gas. The first catalyst layer has an inner surface defining macropores.
Further reduction in NOx emission amount and total hydrocarbon (THC) emission amount is desired. Therefore, the present disclosure provides an exhaust gas purification device that allows reducing a NOx emission amount and a THC emission amount.
The present disclosure includes the following aspects.
the pore connectivity of the second catalyst layer (%)=(S2/900)×100 (1),
the pore connectivity of the first catalyst layer (%)=(S1/900)×100 (2),
the pore connectivity of the third catalyst layer (%)=(S3/900)×100 (3),
the complexity of pores=L2/S (4),
The exhaust gas purification device of the present disclosure can reduce a NOx emission amount and a THC emission amount.
The following will describe embodiments of the present disclosure with reference to the drawings. In the drawings referred in the following description, same reference numerals may be used for the same members or members having similar functions, and their repeated descriptions may be omitted in some cases. For convenience of explanation, a dimensional ratio in the drawings may differ from the actual ratio, and a part of a member may be omitted from the drawing in some cases. A numerical range expressed herein using the term “to” includes values described before and after the term “to” as the lower limit value and the upper limit value, respectively. Upper limit values and lower limit values of numerical ranges described herein can be appropriately combined. The term “on” herein includes both of “directly on” and “indirectly on” insofar as it is not especially specified in the context. The terms “comprise”, “include”, and “contain” herein mean that an additional component may be contained, and encompass the term “consisting essentially of” and the term “consisting of.” The term “consisting essentially of” means that an additional component having substantially no adverse effect may be contained. The term “consisting of” means including only described materials, it does not exclude inclusion of inevitable impurities.
An exhaust gas purification device 100 according to the embodiment will be described with reference to
The shape of the substrate 10 is not specifically limited. However, for example, as illustrated in
For example, the substrate 10 may be formed of a ceramic material having a high heat resistance, such as cordierite (2MgO·2Al2O3·5SiO2), alumina, zirconia, and silicon carbide, or a metal foil, such as a stainless-steel foil. From an aspect of cost, the substrate 10 may be made of cordierite.
In
(2) First Catalyst Layer 20
The first catalyst layer 20 lies on the substrate 10 across a first region X extending between the upstream end I and a first position P, which is at a first distance La from the upstream end I toward the downstream end J (that is, in the flow direction of the exhaust gas). The first catalyst layer 20 need only extend across at least the first region X and may extend beyond the first position P.
The first catalyst layer 20 contains first catalyst particles. The first catalyst particles mainly function as a catalyst for oxidizing HC. The first catalyst particles may be, for example, particles of at least one metal selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os), iridium (Ir), silver (Ag), and gold (Au), and may be particles of at least one metal selected from Pt or Pd in some embodiments. The amount of the first catalyst particles contained in the first catalyst layer 20 may be, for example, 0.1 g/L to 10 g/L based on a substrate capacity in the first region X, may be 1 g/L to 9 g/L based on the substrate capacity in the first region X in some embodiments, and may be 3 g/L to 7 g/L based on the substrate capacity in the first region X in some embodiments. This allows the exhaust gas purification device 100 to have a sufficiently high exhaust gas purification performance.
The first catalyst particles may be loaded on catalytic support particles. The first catalyst particles can be loaded by any loading method such as an impregnation loading method, an adsorption loading method, and a water-absorption loading method.
The catalytic support particles may contain a metal oxide. Examples of the metal oxide include oxide of at least one metal selected from the group consisting of metals of the group 3, the group 4, and the group 13 in the periodic table of elements, and lanthanoid-based metals. More specifically, examples include oxide of at least one metal selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), europium (Eu), lutetium (Lu), titanium (Ti), zirconium (Zr), and aluminum (Al). The metal oxide may be oxide of at least one metal selected from the group consisting of Y, La, Ce, Nd, Ti, Zr, and Al in some embodiments. When the metal oxide is an oxide of two or more metals, the catalytic support particles may be particles containing a mixture of two or more metal oxides, may be particles containing a composite oxide containing two or more metals, or may be particles containing a mixture of at least one metal oxide and at least one composite oxide.
The catalytic support particles may contain particles that function as an Oxygen Storage Capacity (OSC) material that stores oxygen in the atmosphere under oxygen excess atmosphere and releases oxygen under oxygen deficient atmosphere. Examples of the OSC material include ceria (CeO2), composite oxides of ceria and another oxide (for example, a Ce—Zr-based composite oxide, which is a composite oxide of ceria and zirconia (ZrO2), and an Al—Ce—Zr-based composite oxide, which is a composite oxide of alumina (Al2O3), ceria, and zirconia) and materials obtained by adding an additive to them. In particular, a Ce—Zr-based composite oxide may be used as an OSC material because the Ce—Zr-based composite oxide has high oxygen storage capacity and is relatively inexpensive. The additive may be, for example, at least one of lanthana (La2O3), yttria (Y2O3), neodymia (Nd2O3), or praseodymia (Pr6O11), and these materials allow the heat resistance of an OSC material to improve. The additive may form a composite oxide together with a main component of an OSC material.
The first catalyst layer 20 may further contain another optional ingredient. Examples of another optional ingredient include, for example, a binder and an additive.
The first catalyst layer 20 may be provided with pores (not illustrated). This improves the diffusibility of the exhaust gas in the first catalyst layer 20, thus allowing efficient purification of the exhaust gas.
Pore connectivity of the first catalyst layer 20 expressed by formula (2) below may be 5% to 35%,
Pore connectivity of first catalyst layer (%)=(S1/900)×100 (2),
wherein S1 represents the mean value of the sum of the areas (μm2) of the pores that intersect or are in contact with an outer edge of a 30 μm square region and fall within the 30 μm square region (hereinafter, the sum of the areas of such pores is referred to as a “connected pore area”) in a cross-sectional backscattered electron image of the first catalyst layer 20. This can improve the exhaust gas purification performance of the exhaust gas purification device 100. The connected pore area can be measured using image analysis software, such as ImageJ. The mean value S1 of the connected pore area can be determined by measuring the connected pore areas at 10 or more randomly selected points and calculating the arithmetic mean of the measured connected pore areas.
In addition, the ratio (S1/Sa1) of the mean value S1 of the connected pore area to a mean value Sa1 of the sum of the areas (μm2) of all pores included in the above-described 30 μm square region (hereinafter, the sum of the areas of all the pores is referred to as a “total pore area”) may be 35% to 85%. The total pore area can be measured using image analysis software, such as ImageJ. The mean value Sa1 of the total pore area can be determined by measuring the total pore areas at 10 or more randomly selected points and calculating the arithmetic mean of the measured total pore areas.
In the cross-sectional backscattered electron image of the first catalyst layer 20, the mean value of pore areas may be 0.7 μm2 to 9.0 μm2. The mean value of area-equivalent circle diameters of the pores may be 0.7 μm to 2 μm. The mean value of pore perimeters may be 4.0 μm to 12 μm. The mean value of the pore areas, the mean value of the area-equivalent circle diameters of the pores, and the mean value of the pore perimeters herein can be determined as follows. Image analysis software, such as ImageJ, is used to select 10 or more pores that have a size greater than the resolutions of the backscattered electron image and the image analysis software and are not in contact with the outer edge of the image. The area, area-equivalent circle diameter, and perimeter of each of these pores are measured. Then, the arithmetic means of the measured values are calculated.
Further, in the cross-sectional backscattered electron image of the first catalyst layer 20, the complexity of the pores expressed by formula (4) below may be 12.6 to 19.0,
Complexity of pores=L2/S (4),
wherein S represents the mean value of the areas of the pores not in contact with the outer edge of the cross-sectional backscattered electron image, and L represents the mean value of the perimeters of the pores not in contact with the outer edge of the cross-sectional backscattered electron image.
In some embodiments, the pore connectivity of the first catalyst layer 20 may be 5% or more and less than 10%. In addition, the ratio (S1/Sa1) of the mean value S1 of the connected pore area to the mean value Sa1 of the total pore area may be 35% or more and less than 50%. In the cross-sectional backscattered electron image of the first catalyst layer 20, the mean value of the pore areas may be 0.7 μm2 or more and less than 2.0 μm2. The mean value of the area-equivalent circle diameters of the pores may be 0.7 μm or more and less than 1.5 μm. The mean value of the pore perimeters may be 4.0 μm or more and less than 6 μm. The complexity of the pores may be more than 15.0 and 19.0 or less. When the first catalyst layer 20 has such a pore structure, delamination between the first catalyst layer 20 and the second catalyst layer 30 can be avoided or reduced. The first catalyst layer 20 having such a pore structure can be formed using a pore-forming material.
The first catalyst layer 20 can be formed as follows, for example.
First, a slurry containing a first catalyst particle precursor and catalytic support powder is prepared. Alternatively, a slurry containing catalytic support powder on which the first catalyst particles are preliminarily loaded may be prepared. The slurry may further contain a pore-forming material, a binder, an additive, or the like. Properties of the slurry, for example, viscosity and a particle diameter of a solid component may be appropriately adjusted. The prepared slurry is applied to the substrate 10 in the first region X. For example, the substrate 10 is dipped in the slurry from the upstream end I side up to a depth corresponding to the first distance La, and after a predetermined time has elapsed, the substrate 10 is drawn from the slurry, thus allowing the substrate 10 in the first region X to be coated with the slurry. Alternatively, the slurry may be poured through the upstream end I of the substrate 10 into the cells 14, and blown with a blower from the upstream end I to be spread toward the downstream end J, thus allowing the substrate 10 to be coated with the slurry. Next, the slurry is heated at a predetermined temperature for a predetermined period, thus vaporizing a solvent in the slurry layer and dissipating the pore-forming material when the slurry layer contains the pore-forming material. When the pore-forming material is dissipated, pores having the shapes corresponding to the shapes of the pore-forming material are formed at portions where the pore-forming material existed. Accordingly, the first catalyst layer 20 is formed on the substrate 10 in the first region X.
As the pore-forming material, a fibrous pore-forming material may be used. Examples of the fibrous pore-forming material include a polyethylene terephthalate (PET) fiber, an acrylic fiber, a nylon fiber, a rayon fiber, and a cellulose fiber. From a perspective of a balance between ease of processing and dissipation temperature, the pore-forming material may be at least one selected from the group consisting of the PET fiber and the nylon fiber.
As the first catalyst particle precursor, an appropriate inorganic acid salt, such as hydrochloride, nitrate, phosphate, sulfate, borate, and hydrofluoride salt, of the metal constituting the first catalyst particles can be used.
(3) Second Catalyst Layer 30
The second catalyst layer 30 lies on the first catalyst layer 20 across the first region X. The second catalyst layer 30 need only extend across at least the first region X and may extend beyond the first position P. Outside the first region X, the second catalyst layer 30 may be formed directly on the substrate 10 or may be formed indirectly on the substrate 10.
The second catalyst layer 30 contains second catalyst particles. The second catalyst particles mainly function as a catalyst for reducing NOx. The second catalyst particles may be, for example, particles of at least one metal selected from the group consisting of rhodium (Rh), platinum (Pt), palladium (Pd), ruthenium (Ru), osmium (Os), iridium (Ir), silver (Ag), and gold (Au), and especially may be Rh particles. The metal constituting the second catalyst particles may be different from the metal constituting the first catalyst particles. The amount of the second catalyst particles contained in the second catalyst layer 30 may be, for example, 0.05 g/L to 5 g/L, 0.1 g/L to 2.5 g/L, 0.2 g/L to 1.2 g/L, or 0.4 g/L to 0.6 g/L based on the substrate capacity in the first region X. This allows the exhaust gas purification device 100 to have a sufficiently high exhaust gas purification performance.
The second catalyst particles may be loaded on catalytic support particles. The second catalyst particles can be loaded by any loading method such as an impregnation loading method, an adsorption loading method, and a water-absorption loading method. The catalytic support particles usable in the second catalyst layer 30 are similar to the catalytic support particles usable in the first catalyst layer 20.
The second catalyst layer 30 may further contain another optional ingredient. Examples of another optional ingredient include, for example, a binder and an additive.
The second catalyst layer 30 is provided with pores 32. This improves the diffusibility of the exhaust gas in the second catalyst layer 30, thus allowing efficient purification of the exhaust gas.
Pore connectivity of the second catalyst layer 30 expressed by formula (1) below may be 5% to 35%,
Pore connectivity of second catalyst layer (%)=(S2/900)×100 (1),
wherein S2 represents the mean value of the sum of the areas (μm2) of the pores 32 that intersect or are in contact with an outer edge of a 30 μm square region and fall within the 30 μm square region (hereinafter the sum of the areas of such pores is referred to as a “connected pore area”) in a cross-sectional backscattered electron image of the second catalyst layer 30. When the pore connectivity of the second catalyst layer 30 is 5% or more, the diffusibility of the exhaust gas in the second catalyst layer 30 is further improved. This allows reduction in a NOx emission amount and a THC emission amount from the exhaust gas purification device 100. When the pore connectivity of the second catalyst layer 30 is 35% or less, delamination of a part or all of the second catalyst layer 30 can be avoided or reduced, as well as pressure loss by the exhaust gas purification device 100 can be reduced. The connected pore area can be measured using image analysis software, such as ImageJ. The mean value S2 of the connected pore area can be determined by measuring the connected pore areas at 10 or more randomly selected points and calculating the arithmetic mean of the measured connected pore areas.
In addition, the ratio (S2/Sa2) of the mean value S2 of the connected pore area to a mean value Sa2 of the sum of the areas (μm2) of all pores 32 included in the above-described 30 μm square region (hereinafter, the sum of the areas of all the pores is referred to as a “total pore area”) may be 35% to 85%. The total pore area can be measured using image analysis software, such as ImageJ. The mean value Sa2 of the total pore area can be determined by measuring the total pore areas at 10 or more randomly selected points and calculating the arithmetic mean of the measured total pore areas.
In the cross-sectional backscattered electron image of the second catalyst layer 30, the mean value of the areas of the pores 32 may be 0.7 μm2 to 9.0 μm2. The mean value of the area-equivalent circle diameters of the pores 32 may be 0.7 μm to 2 μm. The mean value of the perimeters of the pores 32 may be 4.0 μm to 12 μm. The complexity of the pores 32 defined by the above formula (4) may be 12.6 to 19.0. The mean value of the areas of the pores 32, the mean value of the area-equivalent circle diameters of the pores 32, and the mean value of the perimeters of the pores 32 can be determined by the method similar to that of the first catalyst layer 20.
In some embodiments, the pore connectivity of the second catalyst layer 30 may be 10% to 35%. This can further reduce the NOx emission amount and the THC emission amount from the exhaust gas purification device 100. The second catalyst layer 30 having such high pore connectivity can be formed by controlling the particle diameter of a solid component in a slurry used for forming the second catalyst layer 30. When the pores 32 are formed using a pore-forming material, use of a large amount of pore-forming material should be avoided, otherwise cracks may be occurred in the substrate 10. Therefore, it is difficult to obtain such high pore connectivity when the pores 32 are formed using the pore-forming material. In addition, in these embodiments, the ratio (S2/Sa2) of the mean value S2 of the connected pore area to the mean value Sa2 of the total pore area may be 50% to 85%. In the cross-sectional backscattered electron image of the second catalyst layer 30, the mean value of the areas of the pores 32 may be 2.0 μm2 to 9.0 μm2. The mean value of the area-equivalent circle diameters of the pores 32 may be 1.5 μm to 2 μm. The mean value of the perimeters of the pores 32 may be 6 μm to 12 μm. The complexity of the pores 32 defined by the above formula (4) may be 12.6 to 15.0.
The second catalyst layer 30 may have a thickness of 15 μm to 65 μm. In this case, the NOx emission amount and the THC emission amount from the exhaust gas purification device 100 are further reduced. In particular, the second catalyst layer 30 may have a thickness within a range of 35 μm to 65 μm or 40 μm to 65 μm. In this case, the NOx emission amount and the THC emission amount from the exhaust gas purification device 100 are significantly reduced.
The second catalyst layer 30 can be formed as follows, for example.
First, a slurry containing a second catalyst particle precursor and catalytic support powder is prepared. Alternatively, a slurry containing catalytic support powder on which the second catalyst particles are preliminarily loaded may be prepared. The slurry may further contain a pore-forming material, a binder, an additive, or the like. Properties of the slurry, for example, viscosity and a particle diameter of a solid component may be appropriately adjusted. For example, the particle diameter of the solid component can be adjusted by pulverization conditions (for example, pulverization period) of the solid component using a stirrer, a pulverizer, a bead mill, a ball mill, or the like. The prepared slurry is applied to the substrate 10, on which the first catalyst layer 20 has been preliminarily formed, in the first region X. For example, the substrate 10 is dipped in the slurry from the upstream end I side up to a depth corresponding to the first distance La, and after a predetermined time has elapsed, the substrate 10 is drawn from the slurry, thus allowing the slurry to be applied on the first catalyst layer 20. Alternatively, the slurry may be poured through the upstream end I of the substrate 10 into the cells 14, and blown with a blower from the upstream end I to be spread toward the downstream end J, thus allowing the slurry to be applied on the first catalyst layer 20. Next, the slurry is heated at a predetermined temperature for a predetermined period, thus vaporizing a solvent in the slurry layer and dissipating the pore-forming material when the slurry layer contains the pore-forming material. When the pore-forming material is dissipated, the pores 32 having the shapes corresponding to the shapes of the pore-forming material are formed at portions where the pore-forming material existed. Accordingly, the second catalyst layer 30 is formed on the first catalyst layer 20 in the first region X.
(3) Third Catalyst Layer 40
The third catalyst layer 40 lies on the substrate 10 across the second region Y extending between the downstream end J and a second position Q, which is at a second distance Lb from the downstream end J toward the upstream end I (that is, in a direction opposite to the flow direction of the exhaust gas). While the second position Q is positioned downstream with respect to the first position P in
The third catalyst layer 40 contains third catalyst particles. The third catalyst particles mainly function as a catalyst for reducing NOx. The third catalyst particles may be, for example, particles of at least one metal selected from the group consisting of rhodium (Rh), platinum (Pt), palladium (Pd), ruthenium (Ru), osmium (Os), iridium (Ir), silver (Ag), and gold (Au), and especially may be Rh particles. The metal constituting the third catalyst particles may be different from the metal constituting the first catalyst particles, and may be the same as the metal constituting the second catalyst particles. The amount of the third catalyst particles contained in the third catalyst layer 40 may be, for example, 0.05 g/L to 5 g/L, 0.1 g/L to 2.5 g/L, 0.2 g/L to 1.2 g/L, or 0.4 g/L to 0.6 g/L based on the substrate capacity in the second region Y. This allows the exhaust gas purification device 100 to have a sufficiently high exhaust gas purification performance.
The third catalyst particles may be loaded on catalytic support particles. The third catalyst particles can be loaded by any loading method such as an impregnation loading method, an adsorption loading method, and a water-absorption loading method. The catalytic support particles usable in the third catalyst layer 40 are similar to the catalytic support particles usable in the first catalyst layer 20.
The third catalyst layer 40 may further contain another optional ingredient. Examples of another optional ingredient include, for example, a binder and an additive.
The third catalyst layer 40 may be provided with pores (not illustrated). This improves the diffusibility of the exhaust gas in the third catalyst layer 40, thus allowing the efficient purification of the exhaust gas.
Pore connectivity of the third catalyst layer 40 expressed by formula (3) below may be 5% to 35%,
Pore connectivity of third catalyst layer (%)=(S3/900)×100 (3),
wherein S3 represents the mean value of the sum of the areas (μm2) of the pores that intersect or are in contact with an outer edge of a 30 μm square region and fall within the 30 μm square region (hereinafter, the sum of the areas of such pores is referred to as a “connected pore area”) in a cross-sectional backscattered electron image of the third catalyst layer 40. This can reduce the NOx emission amount from the exhaust gas purification device 100. The connected pore area can be measured using image analysis software, such as ImageJ. The mean value S3 of the connected pore area can be determined by measuring the connected pore areas at 10 or more randomly selected points and calculating the arithmetic mean of the measured connected pore areas.
In addition, the ratio (S3/Sa3) of the mean value S3 of the connected pore area to a mean value Sa3 of the sum of the areas (μm2) of all pores included in the above-described 30 μm square region (hereinafter, the sum of the areas of all the pores is referred to as a “total pore area”) may be 35% to 85%. The total pore area can be measured using image analysis software, such as ImageJ. The mean value Sa3 of the total pore area can be determined by measuring the total pore areas at 10 or more randomly selected points and calculating the arithmetic mean of the measured total pore areas.
In the cross-sectional backscattered electron image of the third catalyst layer 40, the mean value of pore areas may be 0.7 μm2 to 9.0 μm2. The mean value of area-equivalent circle diameters of the pores may be 0.7 μm to 2 μm. The mean value of pore perimeters may be 4.0 μm to 12 μm. The complexity of the pores defined by the above formula (4) may be 12.6 to 19.0. The mean value of the pore areas, the mean value of the area-equivalent circle diameters of the pores, and the mean value of the pore perimeters can be determined by the method similar to that of the first catalyst layer 20.
In some embodiments, the pore connectivity of the third catalyst layer 40 may be 10% to 35%. This can further reduce the NOx emission amount and the THC emission amount from the exhaust gas purification device 100. The third catalyst layer 40 having such high pore connectivity can be formed by controlling the particle diameter of a solid component in a slurry used for forming the third catalyst layer 40. When the pores are formed using a pore-forming material, use of a large amount of pore-forming material should be avoided, otherwise cracks may be generated in the substrate 10. Therefore, it is difficult to obtain such high pore connectivity when the pores are formed using the pore-forming material. In addition, in these embodiments, the ratio (S3/Sa3) of the mean value S3 of the connected pore area to the mean value Sa3 of the total pore area may be 50% to 85%. In the cross-sectional backscattered electron image of the third catalyst layer 40, the mean value of the pore areas may be 2.0 μm2 to 9.0 μm2. The mean value of the area-equivalent circle diameters of the pores may be 1.5 μm to 2 μm. The mean value of the pore perimeters may be 6 μm to 12 μm. The complexity of the pores defined by the above formula (4) may be 12.6 to 15.0.
The third catalyst layer 40 can be formed as follows, for example.
First, a slurry containing a third catalyst particle precursor and catalytic support powder is prepared. Alternatively, a slurry containing catalytic support powder on which the third catalyst particles are preliminarily loaded may be prepared. The slurry may further contain a pore-forming material, a binder, an additive, or the like. Properties of the slurry, for example, viscosity and a particle diameter of a solid component may be appropriately adjusted. The prepared slurry is applied to the substrate 10 in the second region Y. For example, the substrate 10 is dipped in the slurry from the downstream end J side up to a depth corresponding to the second distance Lb, and after a predetermined time has elapsed, the substrate 10 is drawn from the slurry, thus allowing the substrate 10 in the second region Y to be coated with the slurry. Alternatively, the slurry may be poured through the downstream end J of the substrate 10 into the cells 14, and blown with a blower from the downstream end J to be spread toward the upstream end I, thus allowing the substrate 10 to be coated with the slurry. Next, the slurry is heated at a predetermined temperature for a predetermined period, thus vaporizing a solvent in the slurry layer and dissipating the pore-forming material when the slurry layer contains the pore-forming material. When the pore-forming material is dissipated, pores having the shapes corresponding to the shapes of the pore-forming material are formed at portions where the pore-forming material existed. Accordingly, the third catalyst layer 40 is formed on the substrate 10 in the second region Y. Note that the third catalyst layer 40 may be formed before forming the first catalyst layer 20, may be formed after forming the first catalyst layer 20 and before forming the second catalyst layer 30, or may be formed after forming the second catalyst layer 30.
The pore-forming material usable for forming the third catalyst layer 40 is similar to the pore-forming material usable in the formation of the first catalyst layer 20.
As the third catalyst particle precursor, an appropriate inorganic acid salt, such as hydrochloride, nitrate, phosphate, sulfate, borate, and hydrofluoride salt, of the metal constituting the third catalyst particles can be used.
The exhaust gas purification device 100 according to the embodiment is applicable to various vehicles that include internal combustion engines.
The present disclosure is not limited to the above-described embodiments. The present disclosure can be subjected to various kinds of changes, additions, and deletions without departing from the technical idea or the technical scope of the present disclosure described in the claims.
The following will specifically describe the present disclosure with the examples, but the present disclosure is not limited to these examples.
(1) Materials Used in Examples and Comparative Examples
a) Substrate (Honeycomb Substrate)
b) Material 1
c) Material 2
d) Material 3
e) Material 4
f) Material 5
g) Material 6
h) Material 7
(2) Manufacturing Exhaust Gas Purification Device
The material 1, the material 3, the material 5, the material 7, and an Al2O3-based binder were added to distilled water being stirred in an attritor to pulverize each material, and a polyethylene terephthalate fiber as a fibrous pore-forming material was further added and mixed to prepare a suspended slurry 1. Next, the prepared slurry 1 was poured through one end (upstream end) of the substrate into the cells, and excess slurry was blown off with a blower. Consequently, the partition wall of the substrate was coated with the slurry 1 in the first region between the one end of the substrate and the first position, which was at a distance of 50% of the substrate total length from the one end of the substrate toward the other end (downstream end) of the substrate. The substrate was placed in a drying machine whose inside was held at 120° C. for two hours to vaporize water contained in the slurry 1. Next, the substrate was baked in an electric furnace at 500° C. for two hours. Thus, a first catalyst layer was formed.
At this time, the amount of the material 1 contained in the first catalyst layer was 50 g/L based on a substrate capacity in the first region, the amount of the material 3 contained in the first catalyst layer was 50 g/L based on the substrate capacity in the first region, the amount of Pd particles contained in the first catalyst layer as the first catalyst particles derived from the material 5 was 5 g/L based on the substrate capacity in the first region, and the amount of the material 7 contained in the first catalyst layer was 5 g/L based on the substrate capacity in the first region.
Next, the material 1, the material 2, the material 4, the material 6, and the Al2O3-based binder were added to distilled water being stirred in an attritor to pulverize each material, and a suspended slurry 2 was prepared. Next, the prepared slurry 2 was poured through the other end (downstream end) of the substrate into the cells, and excess slurry was blown off with a blower. Consequently, the partition wall of the substrate was coated with the slurry 2 in the second region between the other end of the substrate and the second position, which was at a distance of 50% of the substrate total length from the other end of the substrate toward the one end (upstream end) of the substrate. The substrate was placed in a drying machine whose inside was held at 120° C. for two hours to vaporize water contained in the slurry 2. Next, the substrate was baked in an electric furnace at 500° C. for two hours. Thus, a third catalyst layer was formed.
At this time, the amount of the material 1 contained in the third catalyst layer was 50 g/L based on the substrate capacity in the second region, the amount of the material 2 contained in the third catalyst layer was 50 g/L based on the substrate capacity in the second region, the amount of the material 4 contained in the third catalyst layer was 50 g/L based on the substrate capacity in the second region, and the amount of Rh particles contained in the third catalyst layer as the third catalyst particles derived from the material 6 was 0.5 g/L based on the substrate capacity in the second region.
Next, the material 1, the material 2, the material 4, the material 6, and the Al2O3-based binder were added to distilled water being stirred in an attritor to pulverize each material, and a suspended slurry 3 was prepared. Next, the prepared slurry 3 was poured through one end (upstream end) of the substrate into the cells, and excess slurry was blown off with a blower. Consequently, a layer of the slurry 3 was formed in the first region between the one end of the substrate and the first position, which was at a distance of 50% of the substrate total length from the one end of the substrate toward the other end (downstream end) of the substrate. The substrate was placed in a drying machine whose inside was held at 120° C. for two hours to vaporize water contained in the slurry 3. Next, the substrate was baked in an electric furnace at 500° C. for two hours. Thus, a second catalyst layer was formed.
At this time, the thickness of the second catalyst layer, the total mass (total application amount) of the second catalyst layer based on the substrate capacity in the first region, and the amounts of the material 1, the material 2, the material 4, and Rh particles as the second catalyst particles derived from the material 6 contained in the second catalyst layer based on the substrate capacity in the first region, were as described in Table 1.
Thus, exhaust gas purification devices of Comparative Examples 1 and 2 were manufactured.
An exhaust gas purification device was manufactured similarly to Comparative Example 1 except that the amount of Rh derived from the material 6 and contained in the third catalyst layer was 1.0 g/L based on the substrate capacity in the second region, and that the second catalyst layer was not formed.
An exhaust gas purification device was manufactured similarly to Comparative Example 1 except that the period to pulverize the slurry 3 for forming the second catalyst layer was shorter than that of Comparative Example 1, and that the particle size of the materials contained in the slurry 3 was larger than that of Comparative Example 1.
Exhaust gas purification devices were manufactured similarly to Example 1 except that the thickness of the second catalyst layer, the total mass (total application amount) of the second catalyst layer based on the substrate capacity in the first region, and the amounts of the material 1, the material 2, the material 4, and Rh particles as the second catalyst particles derived from the material 6 contained in the second catalyst layer based on the substrate capacity in the first region, were as described in Table 1.
An exhaust gas purification device was manufactured similarly to Comparative Example 1 except that a polyethylene terephthalate fiber as a fibrous pore-forming material was added to the slurry 3.
An exhaust gas purification device was manufactured similarly to Example 1 except that the period to pulverize the slurry 2 for forming the third catalyst layer was shorter than that of Example 1, and that the particle size of the materials contained in the slurry 2 was larger than that of Example 1.
Exhaust gas purification devices were manufactured similarly to Example 6 except that the thickness of the second catalyst layer, the total mass (total application amount) of the second catalyst layer based on the substrate capacity in the first region, and the amounts of the material 1, the material 2, the material 4, and Rh particles as the second catalyst particles derived from the material 6 contained in the second catalyst layer based on the substrate capacity in the first region, were as described in Table 1.
(3) Structure Evaluation
In each of the exhaust gas purification devices of Comparative Example 1 and Examples 1 and 5, an approximately 1 cm cube of sample was extracted from a portion including the second catalyst layer and buried in a room temperature-curable epoxy resin. Wet sanding was used to prepare a cross-section, which was perpendicular or parallel to the flow direction of an exhaust gas, of the second catalyst layer. The sanded surface was subjected to conductive treatment with carbon.
The cross-section of the second catalyst layer was observed under the following conditions using a scanning electron microscope (SEM, “SU7000” manufactured by Hitachi High-Tech Corporation).
At least 10 backscattered electron images of the cross-section, which was perpendicular or parallel to the flow direction of an exhaust gas, of the second catalyst layer were obtained. The resolution of a backscattered electron image under the above-described conditions was 0.05 μm/pixel.
Image analysis software (ImageJ) was used to binarize each backscattered electron image and discriminate pores from others (such as a catalyst and a binder). In the binarized image of each backscattered electron image (hereinafter referred to as a “binarized image”), pores having an area of at least 0.02 μm2, which was the resolution of the backscattered electron image, and not in contact with the outer edge of the image were extracted. The area and perimeter of each pore were determined, and the complexity of each pore was calculated by dividing the square of the perimeter by the area. When the cross-section of a pore is a perfect circle, the pore should have a minimum complexity of 4π. However, as a result of the calculation, among the pores having an area less than 0.05 μm2 (equivalent to a circular equivalent diameter of approximately 0.25 μm), some pores had a complexity value of less than 4π. Therefore, the resolution by the analysis method in the example was determined as an area of 0.05 μm2 (circular equivalent diameter of approximately 0.25 μm).
In each binarized image, pores having the area of at least 0.05 μm2, which was the analysis resolution, and not in contact with the outer edge of the image were extracted.
Complexity of pores=L2/S,
wherein S represents the mean value of the areas of the pores, and L represents the mean value of the perimeters of the pores. Table 2 shows the results.
In each binarized image, a 30 μm square region was randomly selected. Furthermore, 30 μm square regions at positions parallel-shifted in the up, down, left, and right directions by 10 μm from the first selected region were also selected. The sum of the areas of all pores (i.e., total pore area) included in each of these five regions was measured by the image analysis software (ImageJ). The sum of the areas of pores not in contact with the outer edge of each region was also measured. The sum of the areas of the pores not in contact with the outer edge of each region was subtracted from the total pore area to obtain a value. This value corresponds to the sum of the areas of the pores that intersect or are in contact with the outer edge of each region and fall within the region (i.e., connected pore area). The arithmetic mean of the connected pore areas determined in the respective regions was calculated to obtain the mean value S2 of the connected pore areas. The mean value S2 of the connected pore areas was divided by the area of each region (i.e., 900 μm2) to obtain a pore connectivity. Table 3 shows the results. The second catalyst layer of Example 5 formed using a pore-forming material had a higher pore connectivity than the second catalyst layer of Comparative Example 1. The second catalyst layer of Example 1 formed by the shortened pulverization period of the slurry had a higher pore connectivity than the second catalyst layers of Comparative Example 1 and Example 5.
Additionally, the arithmetic mean of the total pore areas in the respective regions described above was calculated to obtain the mean value Sa2 of the total pore areas. Table 3 shows the ratio (S2/Sa2) of the mean value S2 of the connected pore areas to the mean value Sa2 of the total pore areas.
(4) Exhaust Gas Purification Performance Evaluation
The exhaust gas purification devices of Examples 1 to 5 and Comparative Examples 1 to 3 were each arranged immediately below an engine. An engine operation condition was set such that the catalyst bed temperature of each of the exhaust gas purification devices was 950° C. Over 50 hours, an air-fuel ratio feedback control and a fuel cut were alternately repeated.
Then, the engine operation condition was set such that the temperature of a gas introduced into each of the exhaust gas purification devices was 550° C. The air-fuel ratio (A/F) of a mixed gas supplied to the engine was set to 14.4, and an exhaust gas from the engine was introduced into each of the exhaust gas purification devices. After the temperature of the gas introduced into each of the exhaust gas purification devices stabilized at 550° C., the air-fuel ratio (A/F) of the mixed gas supplied to the engine was alternately switched between 14.1 (rich (i.e., excess fuel)) and 15.1 (lean (i.e., excess oxygen)) at a cycle time of three minutes. At three minutes after the A/F was switched from 15.1 to 14.1 for the third time, the THC emission amount and the NOx emission amount were measured.
As understood from
In particular, the exhaust gas purification devices of Examples 1 to 4 in which the pulverization periods of the slurry 3 were shortened exhibited even lower THC emission amounts. It is considered that this is due to the particularly high pore connectivity of the second catalyst layer (see Table 3).
Further, the exhaust gas purification devices of Examples 1 to 3, which had the second catalyst layers having a thickness of 15 μm to 65 μm, exhibited particularly low THC emission amounts. This result indicates that when the thickness of the second catalyst layer was 65 μm or less, it was easy enough for the exhaust gas to pass through the second catalyst layer to reach the first catalyst layer. On the other hand, in Comparative Examples 1 to 3, the greater the thickness of the second catalyst layer, the greater the THC emission amount, and in particular, a significantly high THC emission amount was exhibited when the thickness of the second catalyst layer was 36 μm or more. This suggests the followings. In Comparative Examples 1 and 2, the diffusibility of the exhaust gas in the second catalyst layer was poor. Therefore, the greater the thickness of the second catalyst layer, the lower the amount of the exhaust gas reaching the first catalyst layer and the lower the probability of HC in the exhaust gas coming into contact with the Pd particles in the first catalyst layer, resulting in an increase in the amount of HC remaining unoxidized. It is considered that, in particular, when the thickness of the second catalyst layer was 36 μm or more, the exhaust gas reaching the first catalyst layer was significantly reduced.
As understood from
The amount in reduction of the NOx emission amount with an increase in the thickness of the second catalyst layer was greater in Examples 1 to 4 than in Comparative Examples 1 to 3. The inventors consider that this result is caused by the following reason.
In the exhaust gas purification devices of the comparative examples and the examples, the greater the thickness of the second catalyst layer was, the lower the concentration of Rh in the second catalyst layer was. The lower the concentration of Rh in the second catalyst layer was, the less the coarsening of the Rh particles in the second catalyst layer by heat occurred, and thus the less the decrease of the catalytic activity of the Rh particles was caused. Therefore, the Rh particles in the second catalyst layer having greater thickness were able to deliver higher NOx conversion performance. However, in Comparative Examples 1 to 3, the greater the thickness of the second catalyst layer was, the more HC remained unoxidized in the first catalyst layer (see
As illustrated in
As illustrated in
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-178392 | Nov 2022 | JP | national |
