Patent Application
20240408543
The present invention relates to an exhaust gas purifying system for a gasoline engine. The present invention also relates to an exhaust gas purifying catalyst body suitable for the exhaust gas purifying system for a gasoline engine. The present application claims priority based on Japanese Patent Application No. 2021-163182 filed on Oct. 4, 2021, the entire contents of which application are incorporated herein by reference.
The exhaust gas emitted from a gasoline engine of a vehicle or the like includes toxic substances such as hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NOx). For efficient reaction and removal of these toxic substances from the exhaust gas, exhaust gas purifying catalysts have been used conventionally.
Exhaust gas purifying systems for a gasoline engine, in which a start catalyst (S/C) and an underfloor catalyst (UF/C) are combined to further reduce the emission of NOx have been known (for example, see Patent Literature 1).
[Patent Literature 1] Japanese Patent Application Publication No. 2020-34001.
In recent years, exhaust gas regulations have become stricter and reduction of the NH3 emission from gasoline engine vehicles has been demanded. NH3 is a component that can be generated when NOx is over-reduced by an exhaust gas purifying catalyst. In the exhaust gas purifying systems in which the start catalyst (S/C) and the underfloor catalyst (UF/C) are combined, more NH3 is emitted as the NOx purifying performance is higher. Patent Literature 1 describes that the NH3 purifying performance is improved by introducing a zeolite with NH3 adsorbing capability into an exhaust gas purifying system for a gasoline engine.
However, through the present inventors' earnest examinations, a problem has been found out that, in the conventional exhaust gas purifying system for a gasoline engine including the zeolite with the NH3 adsorbing capability, the NH3 purifying performance deteriorates after duration.
The present invention has been made in view of the above circumstances, and an object is to provide an exhaust gas purifying system for a gasoline engine with high NH3 purifying performance after duration.
An exhaust gas purifying system for a gasoline engine disclosed herein is configured to be disposed in an exhaust path of the gasoline engine. The exhaust gas purifying system includes an upstream catalyst converter including a first catalyst body and a downstream catalyst converter including a second catalyst body. The first catalyst body contains a catalyst precious metal. The second catalyst body has a structure in which an NH3 adsorption layer and a catalyst layer are stacked on a base material. The NH3 adsorption layer of the second catalyst body contains a zeolite as an NH3 adsorber. The catalyst layer of the second catalyst body contains a catalyst precious metal and an OSC material.
The present inventors have discovered the following when completing the exhaust gas purifying system for a gasoline engine disclosed herein. The exhaust gas purifying system for a gasoline engine is used in a high environmental temperature range, and the atmosphere varies between a rich atmosphere and a lean atmosphere. The oxygen concentration is low in a region with an air-fuel ratio in the rich to stoichiometric atmosphere; therefore, the structure of the zeolite with the NH3 adsorbing capability deteriorates under high temperature and accordingly, the NH3 purifying performance after duration decreases.
Thus, in the exhaust gas purifying system for a gasoline engine disclosed herein, the catalyst layer containing the OSC material is stacked on the NH3 adsorption layer containing the zeolite. Therefore, even in the rich to stoichiometric region with the low oxygen concentration, oxygen can be supplied from the OSC material to the NH3 adsorption layer and the structure deterioration of the zeolite can be suppressed. Accordingly, by the exhaust gas purifying system disclosed herein, the exhaust gas purifying system with the high NH3 purifying performance after duration can be provided.
In a preferred aspect of the exhaust gas purifying system for a gasoline engine disclosed herein, the NH3 adsorption layer is stacked on a lower layer side relative to the catalyst layer in the second catalyst body. By such a structure, the exhaust gas purifying system with the higher NH3 purifying performance after duration can be provided.
In a preferred aspect of the exhaust gas purifying system for a gasoline engine disclosed herein, the zeolite is a CHA-type zeolite carrying Cu. By such a structure, the exhaust gas purifying system with the particularly high NH3 purifying performance after duration can be provided.
The exhaust gas purifying system for a gasoline engine disclosed herein may have the following aspects.
A gasoline particulate filter is further provided between the upstream catalyst converter and the downstream catalyst converter in a flowing direction of exhaust gas in the exhaust path.
A gasoline particulate filter is further provided on a downstream side relative to the downstream catalyst converter in the flowing direction of exhaust gas in the exhaust path.
The first catalyst body of the upstream catalyst converter is a tandem type catalyst body including an upstream side catalyst body and a downstream side catalyst body. In this case, a gasoline particulate filter may be further provided between the upstream catalyst converter and the downstream catalyst converter or on a downstream side relative to the downstream catalyst converter. Alternatively, the downstream side catalyst body of the first catalyst body may have a function as a gasoline particulate filter.
The first catalyst body of the upstream catalyst converter has a function as a gasoline particulate filter.
In another aspect, an exhaust gas purifying catalyst body for a gasoline engine disclosed herein includes a base material, an NH3 adsorption layer stacked on the base material, and a catalyst layer stacked on the NH3 adsorption layer. The NH3 adsorption layer contains a zeolite as an NH3 adsorber, and an OSC material. The catalyst layer contains a catalyst precious metal and an OSC material. This exhaust gas purifying catalyst body for a gasoline engine is suitably used for the aforementioned exhaust gas purifying system for a gasoline engine. Here, the NH3 adsorption layer may further contain a catalyst precious metal.
Preferred embodiments of the present invention will be described below with reference to the drawings. Matters that are other than matters particularly mentioned in the present specification and that are necessary for the implementation of the present invention can be grasped as design matters of those skilled in the art based on the prior art in the relevant field. The present invention can be carried out based on the contents disclosed in this specification and technical common sense in the relevant field. In the drawings below, the members and parts with the same operation are denoted with the same reference sign and the overlapping description may be omitted or simplified. The size relation (length, width, thickness, and the like) in each drawing does not always reflect the actual size relation. In the present specification, the notation “A to B” (A and B are arbitrary numerals) for a range signifies a value more than or equal to A and less than or equal to B, and also encompasses the meaning of being “preferably more than A” and “preferably less than B”.
The upstream catalyst converter 10 includes a first catalyst body and a first housing that accommodates the first catalyst body. The downstream catalyst converter 50 includes a second catalyst body and a second housing that accommodates the second catalyst body. The first catalyst body exists on the upstream side relative to the second catalyst body in the flowing direction F of the exhaust gas. The first catalyst body is typically, but not limited to, a startup catalyst (S/C). The second catalyst body exists on the downstream side relative to the first catalyst body 20 in the flowing direction F of the exhaust gas. The second catalyst body is typically, but not limited to, an underfloor catalyst (UF/C). The first housing and the second housing may have a structure that is the same as or similar to that of the housing used for the conventional startup catalyst and underfloor catalyst.
The first catalyst body and the second catalyst body will be described below in detail. The first catalyst body may have a structure that is the same as or similar to that of the conventionally known catalyst body. Accordingly, the second catalyst body is described first.
Examples of the structure of the second catalyst body are illustrated in
The second base material 70 forms the frame of the second catalyst body 60. The second base material 70 is not particularly limited and various materials and various modes that have conventionally been employed in this type of applications can be used. The second base material 70 may be, for example, a ceramic carrier formed of ceramic such as cordierite, aluminum titanate, or silicon carbide, or a metal carrier formed of stainless steel (SUS), a Fe—Cr—Al-based alloy, a Ni—Cr—Al-based alloy, or the like. As illustrated in
In the drawings, a direction X expresses a cylinder axis direction of the second base material 70, X1 expresses the upstream side in the flowing direction F of the exhaust gas, and X2 expresses the downstream side in the flowing direction of the exhaust gas. The second base material 70 includes a plurality of cells (cavities) 72 arrayed regularly in the cylinder axis direction X, and partition walls (ribs) 74 that section the plurality of cells 72. Although not particularly limited, the volume (the apparent volume including the capacity of the cells 72) of the second base material 70 may be generally 0.1 to 10 L, for example 0.5 to 5 L. In addition, an average length (overall length) L of the second base material 70 along the cylinder axis direction X may be generally 10 to 500 mm, for example 50 to 300 mm.
The cell 72 serves as a flow channel for the exhaust gas. The cell 72 extends in the cylinder axis direction X. The cell 72 is a through hole penetrating the second base material 70 in the cylinder axis direction X. The shape, the size, the number, and the like of the cells 72 may be designed in consideration of, for example, the flow rate, the component, and the like of the exhaust gas flowing in the second catalyst body 60. The shape of the cross section of the cell 72 that is orthogonal to the cylinder axis direction X is not limited in particular. The cross-sectional shape of the cell 72 may be, for example, a tetragon such as a square, a parallelogram, a rectangle, or a trapezoid, another polygon (such as a triangle, a hexagon, or an octagon), a wavy shape, a circular shape, or various other geometric shapes. The partition wall 74 faces the cell 72 and sections between the adjacent cells 72. Although not particularly limited, the average thickness of the partition wall 74 (the size in a direction orthogonal to the surface, this definition similarly applies to the description below) may be generally 0.1 to 10 mil (1 mil is equal to about 25.4 μm) and for example, 0.2 to 5 mil from the viewpoint of increasing the mechanical strength, the viewpoint of reducing the pressure loss, or the like. The partition wall 74 may be porous so that the exhaust gas can pass therethrough.
On this second base material 70, the NH3 adsorption layer 80 and the second catalyst layer 90 are stacked. The order of stacking the NH3 adsorption layer 80 and the second catalyst layer 90 is not limited in particular. As illustrated in
The NH3 adsorption layer 80 contains a zeolite as an NH3 adsorber. Therefore, the zeolite contained in the NH3 adsorption layer 80 is a zeolite with NH3 adsorbing capability. Examples of such a zeolite include zeolites carrying transition metal.
The transition metal carried by the zeolite is, for example, at least one kind of transition metal selected from the group consisting of V, Mn, Fe, Co, Ni, Cu, La, Ce, and Ag, preferably at least one kind of transition metal selected from the group consisting of Fe, Cu, and Ag, more preferably Cu and/or Fe, and the most preferably Cu. It should be note that in the present specification, the expression “A and/or B” refers to one of A and B or both A and B.
The zeolite forming a basic skeleton is typically aluminosilicate but may alternatively be silicoaluminophosphate (SAPO). The zeolite preferably includes pores with the size suitable to adsorb NH3. Examples of the structure of the zeolite that is expressed with codes according to International Zeolite Association (IZA) include AEI, AFX, AFT, AST, BEA, BEC, CHA, EAB, ETR, GME, ITE, KFI, LEV, PAU, SAS, SAT, SAV, THO, UFI, ATT, DDR, ERI, IFY, JST, LOV, LTA, OWE, RHO, RSN, SFW, TSC, UEI, VSV, and the like. In particular, AEI, AFX, AFT, AST, BEA, BEC, CHA, EAB, ETR, GME, ITE, KFI, LEV, PAU, SAS, SAT, SAV, THO, and UFI are given and CHA (chabazite) is preferable. It should be noted that the skeleton structure of the zeolite can be checked by, for example, an X-ray diffraction (XRD) method. From the viewpoint of the NH3 adsorbing capability, it is particularly preferable to use a CHA-type zeolite carrying Cu as the zeolite.
The amount of the zeolite in the NH3 adsorption layer 80 is not limited in particular. The amount of the zeolite in the NH3 adsorption layer 80 is preferably 10 mass % or more from the viewpoint of the higher NH3 purifying performance after duration. In a case where the atmosphere variation of the exhaust gas is small, increasing the amount of the zeolite in the NH3 adsorption layer 80 is advantageous in terms of the high NH3 purifying performance after duration. Thus, the amount of the zeolite in the NH3 adsorption layer 80 may be 50 mass % or more or 80 mass % or more.
The NH3 adsorption layer 80 can contain a component other than the aforementioned components as an optional component. Examples of the optional component include an oxygen storage capacity material (so-called OSC material) capable of storing and releasing oxygen. As the OSC material, a known compound that has been known as having the oxygen storage capacity may be used, and specific examples thereof include a metal oxide (Ce-containing oxide) containing ceria (CeO2). The Ce-containing oxide may be ceria or a composite oxide containing ceria and metal oxide other than ceria. From the viewpoints of improving the heat resistance and the durability, and the like, the Ce-containing oxide may be a composite oxide containing at least one of Zr and Al, for example, a ceria (CeO2)-zirconia (ZrO2) composite oxide (CZ composite oxide). From the viewpoints of improving the heat resistance and the like, for example, the CZ composite oxide may further include a rare earth metal oxide such as Nd2O3, La2O3, Y2O3, or Pr6O10.
In a case where the OSC material is the composite oxide containing cerium oxide, the content of cerium oxide is preferably 15 mass % or more and more preferably 20 mass % or more from the viewpoint of achieving the oxygen storage capacity sufficiently. On the other hand, if the content of cerium oxide is too high, the basicity of the OSC material may become too high. Therefore, the content of cerium oxide is preferably 60 mass % or less and more preferably 50 mass % or less.
The amount of the OSC material in the NH3 adsorption layer 80 is not limited in particular. The amount of the OSC material in the NH3 adsorption layer 80 is for example 10 mass % or more and preferably 20 mass % or more. On the other hand, the amount of the OSC material is for example 60 mass % or less and preferably 40 mass % or less.
Another example of the optional component of the NH3 adsorption layer 80 is a catalyst precious metal. When the NH3 adsorption layer 80 contains the catalyst precious metal, the NH3 adsorption layer 80 can also purify the exhaust gas.
Examples of the catalyst precious metal include: platinum group elements such as rhodium (Rh), palladium (Pd), platinum (Pt), ruthenium (Ru), osmium (Os), and iridium (Ir); gold (Au); and silver (Ag). These can be used alone, or two or more kinds thereof may be used in combination. In particular, from the viewpoint of the catalyst performance, at least one kind selected from the group consisting of Pt, Rh, Pd, Ir, and Ru is preferable and at least one kind selected from the group consisting of Pt, Rh, and Pd is more preferable. In a case of using two or more kinds of these, the catalyst precious metal may be an alloy of the two or more kinds of metal species.
The catalyst precious metal may be carried by the aforementioned OSC material, or carried by a non-OSC material (for example, alumina (Al2O3), titania (TiO2), zirconia (ZrO2), silica (SiO2), or the like).
As a still another example of the optional component of the NH3 adsorption layer 80, a binder such as alumina sol and silica sol, various kinds of additives, and the like are given.
The coat amount (that is, forming amount) of the NH3 adsorption layer 80 is not limited in particular. The coat amount is 10 to 200 g/L for example, and may be 100 to 200 g/L per liter of the volume of a part of the base material where the NH3 adsorption layer 80 is formed along the cylinder axis direction X. By satisfying the above range, both the improvement of the purifying performance for the toxic substances and the reduction of the pressure loss can be achieved at a high level. Moreover, the durability and the peeling resistance can be improved.
The thickness of the NH3 adsorption layer 80 is not limited in particular and may be designed as appropriate in consideration of the durability, the peeling resistance, and the like. The thickness of the NH3 adsorption layer 80 is 1 to 100 μm for example, and may be 5 to 100 μm.
The coat width (an average dimension in the cylinder axis direction X) of the NH3 adsorption layer 80 is not limited in particular and may be designed as appropriate in consideration of the size of the second base material 70, the flow rate of the exhaust gas flowing in the second catalyst body 60, and the like. The coat width is for example 10% to 100%, preferably 20% to 100%, and more preferably 30% to 100% of the overall length of the base material in the cylinder axis direction X.
The second catalyst layer 90 contains a catalyst precious metal. The catalyst precious metal is normally carried by a carrier, and thus, the second catalyst layer 90 normally includes a three-way catalyst. The second catalyst layer 90 can be configured similarly to a known catalyst layer including the three-way catalyst.
The catalyst precious metal is a catalyst metal component that purifies the toxic substances in the exhaust gas. Examples of the catalyst precious metal include ones exemplified as the catalyst precious metal that is used for the NH3 adsorption layer 80. One kind of the catalyst precious metal may be used alone, but it is preferable to use two or more kinds thereof in combination. As the catalyst precious metal, from the viewpoint of the catalyst performance, at least two kinds selected from the group consisting of Pt, Rh, Pd, Ir, and Ru are preferable, and a combination of Rh, which has high reduction activity, and Pd and/or Pt, which have high oxidation activity, is more preferable.
The catalyst precious metal is preferably used as microparticles with sufficiently small particle diameter. The average particle diameter of the catalyst precious metal particles (specifically, average value of particle diameters of 20 or more precious metal particles obtained based on a cross-sectional image of the catalyst layer by a transmission electron microscope) is generally about 1 to 15 nm, preferably 10 nm or less, more preferably 7 nm or less, and still more preferably 5 nm or less. Thereby, the contact area of the catalyst precious metal with the exhaust gas can be increased and the purifying performance can be improved further.
The amount of the catalyst precious metal in the second catalyst body 60 (the total amount of the catalyst precious metal in the NH3 adsorption layer 80 and the second catalyst layer 90) is not limited in particular and can be determined as appropriate depending on the kind of catalyst precious metal or the like. The amount of the catalyst precious metal per liter of the volume of the second base material 70 may be, for example, 0.01 g/L or more, 0.03 g/L or more, 0.05 g/L or more, 0.08 g/L or more, or 0.10 g/L or more from the viewpoint of the particularly high exhaust gas purifying performance. From the viewpoint of making the exhaust gas purifying performance and the cost balanced, this amount may be, for example, 5.00 g/L or less, 3.00 g/L or less, 2.00 g/L or less, 1.50 g/L or less, 1.00 g/L or less, 0.80 g/L or less, or 0.50 g/L or less.
It should be noted that in the present specification, “per liter of the volume of the base material” refers to per liter of the entire bulk volume including the capacity of cell paths in addition to the pure volume of the base material. The amount described as (g/L) in the following description represents the amount included in a liter of the volume of the base material.
The second catalyst layer 90 contains the OSC material. Examples of the OSC material contained in the second catalyst layer 90 include ones exemplified as the OSC material that can be used for the NH3 adsorption layer 80.
The OSC material may or may not carry the catalyst precious metal. Some OSC materials may carry the catalyst precious metal while the other OSC materials may not carry the catalyst precious metal.
The second catalyst layer 90 may further include the non-OSC material (that is, material incapable of storing and releasing oxygen), and the catalyst precious metal may be carried by the non-OSC material. Examples of the non-OSC material include alumina (Al2O3), titania (TiO2), zirconia (ZrO2), silica (SiO2), and the like.
Therefore, in the second catalyst layer 90, usually, one of or both the OSC material and the non-OSC material are used as the carrier. The carrier preferably has a large specific surface area, and thus, porous carrier particles are used suitably. The carrier particle has a specific surface area, which is obtained based on a BET method, of preferably 50 to 500 m2/g (particularly, 200 to 400 m2/g) from the viewpoints of the heat resistance and the structure stability. Moreover, the average particle diameter of the carrier particles (specifically, average value of particle diameters of 20 or more carrier particles obtained based on a cross-sectional image of the catalyst layer by a transmission electron microscope) is preferably 1 nm or more and 500 nm or less (particularly, 10 nm or more and 200 nm or less).
The amount of the OSC material in the second catalyst layer 90 is for example 10 mass % or more, preferably 30 mass % or more, and more preferably 40 mass % or more. On the other hand, the amount of the OSC material in the second catalyst layer 90 is for example less than 90 mass %, preferably less than 60 mass %, and more preferably 50 mass % or less.
The amount of the non-OSC material in the second catalyst layer 90 is for example 10 mass % or more, preferably 30 mass % or more, and more preferably 40 mass % or more. On the other hand, the amount of the non-OSC material in the second catalyst layer 90 is for example less than 90 mass %, preferably less than 70 mass %, and more preferably less than 60 mass %.
The second catalyst layer 90 may further include a component other than the aforementioned components. For example, the second catalyst layer 90 may include a metal species such as an alkali metal element, an alkaline earth metal element, a transition metal element, or a rare-earth element. These elements (particularly, alkaline earth element) may be contained as an oxide, a hydroxide, a carbonate, a nitrate, a sulfate, a phosphate, an acetate, a formate, an oxalate, a halide, or the like. In the second catalyst layer 90, it is preferable that the alkaline earth metal element (in particular, Ba), and Pt and/or Pd coexist.
As other optional components of the second catalyst layer 90, a binder such as alumina sol and silica sol, a NOx adsorber with NOx absorbing capability, various kinds of additives such as a stabilizer, and the like are given.
The second catalyst layer 90 may have either a single layer structure or a multilayer structure. In examples illustrated in
When the second catalyst layer 90 has the multilayer structure, the number of layers is not limited in particular. The second catalyst layer 90 may have a two-layer structure including a layer on the base material side (lower layer) and a layer on a surface side (upper layer), or may have a structure of three or more layers including the layer on the base material side (lower layer), the layer on the surface side (upper layer), and one or more intermediate layers existing therebetween. In this multilayer structure, the respective layers may contain different catalyst precious metals.
The second catalyst layer 90 includes a lower layer part 92 corresponding to the layer on the base material side, and an upper layer part 94 provided on the lower layer part 92. In the illustrated example, the upper layer part 94 is also the layer on the exposed surface side of the second catalyst layer 90. Each of the lower layer part 92 and the upper layer part 94 of the second catalyst layer 90 contains the catalyst precious metal. The lower layer part 92 contains Pd as the catalyst precious metal. On the other hand, the upper layer part 94 contains Rh as the catalyst precious metal. In this case, by carrying an oxidizing catalyst and a reducing catalyst with these catalysts separated from each other in a stacking direction, the deterioration of the catalyst precious metal (for example, sintering due to grain growth) can be suppressed, so that the durability of the second catalyst body 60 can be improved further.
The coat amount (that is, forming amount) of the second catalyst layer 90 is not limited in particular. The coat amount is 10 to 500 g/L for example, and may be 100 to 200 g/L per liter of the volume of a part of the base material where the catalyst layer 20 is formed along the cylinder axis direction X. By satisfying the above range, both the improvement of the purifying performance for the toxic substances and the reduction of the pressure loss can be achieved at a high level. Moreover, the durability and the peeling resistance can be improved.
The thickness of the second catalyst layer 90 is not limited in particular and may be designed as appropriate in consideration of the durability, the peeling resistance, and the like. The thickness of the second catalyst layer 90 is 1 to 100 μm for example, and may be 5 to 100 μm.
The coat width (an average dimension in the cylinder axis direction X) of the second catalyst layer 90 is not limited in particular and may be designed as appropriate in consideration of the size of the second base material 70, the flow rate of the exhaust gas flowing in the second catalyst body 60, and the like. The coat width is for example 10% to 100%, preferably 20% to 100%, and more preferably 30% to 100% of the overall length of the base material in the cylinder axis direction X.
The second catalyst body 60 may include a layer other than the NH3 adsorption layer 80 and the second catalyst layer 90.
The second catalyst body 60 can be manufactured in accordance with a known method. For example, a slurry for NH3 adsorption layer formation, which contains a zeolite functioning as the NH3 adsorber, a solvent, and optional components (for example, OSC material, catalyst precious metal source, binder, and the like) is prepared. Moreover, a slurry containing a catalyst precious metal source, an OSC material, a non-OSC material if necessary, a solvent, and other optional components is prepared. Of these slurries, the slurry for the lower layer side is applied to the second base material 70 in accordance with the known method and dried as necessary, which is then fired to form the lower layer. Subsequently, the slurry for the upper layer side is applied onto the lower layer formed on the second base material 70 in accordance with the known method and dried as necessary, which is then fired to form the upper layer. Thus, the second catalyst body 60 can be obtained.
The first catalyst body 20 may have a structure that is the same as or similar to that of the startup catalyst in the known exhaust gas purifying system for a gasoline engine including the startup catalyst (S/C) and the underfloor catalyst (UF/C).
One example of the first catalyst body 20 is illustrated in
In the first embodiment, the straight-flow type base material is used for the first base material 30. However, the first base material 30 is not limited to this, and may be the wall-flow type base material. For example, the first catalyst body 20 may be configured as a catalyst coated type gasoline particulate filter (GPF) by using the wall-flow type base material as the first base material 30, which will be described in an embodiment below.
The first base material 30 may be a ceramic carrier formed of ceramic such as cordierite, aluminum titanate, or silicon carbide, or a metal carrier formed of stainless steel (SUS), a Fe—Cr—Al-based alloy, a Ni—Cr—Al-based alloy, or the like.
Although the first catalyst body 20 includes one first base material 30 in the first embodiment, the structure is not limited to this example. In another example, the first catalyst body 20 may be a tandem type catalyst body including a plurality of the first base materials 30, each of which includes the first catalyst layer 40, as will be described in an embodiment below. In the tandem type catalyst body, the plurality of first base materials 30 may be either of the same kind or different kinds. The plurality of first catalyst layers 40 may have either the same or different compositions.
The first catalyst layer 40 contains the catalyst precious metal. The catalyst precious metal contained in the first catalyst layer 40 may be similar to the catalyst precious metal contained in the second catalyst layer 90 of the second catalyst body 60. The first catalyst layer 40 usually contains the carrier that carries the catalyst precious metal. The carrier contained in the first catalyst layer 40 may be similar to the carrier contained in the second catalyst layer 90 of the second catalyst body 60. The other components contained in the first catalyst layer 40 may be similar to those of the second catalyst layer 90 of the second catalyst body 60.
The first catalyst layer 40 may have either a single layer structure or a multilayer structure. When the first catalyst layer 40 has the single layer structure, the first catalyst layer 40 may include a plurality of regions having different compositions, properties, or the like. In another example, the first catalyst layer 40 may include a front part that is positioned on an upstream side Y1 in a cylinder axis direction Y, and a rear part that is positioned on a downstream side Y2, and the compositions and/or properties may be different between the front part and the rear part. Specifically, for example, the front part and the rear part may contain different precious metals.
When the first catalyst layer 40 has the multilayer structure, the number of layers is not limited in particular. The first catalyst layer 40 may have a two-layer structure including a layer on the base material side (lower layer) and a layer on a surface side (upper layer), or may have a structure of three or more layers including the layer on the base material side (lower layer), the layer on the surface side (upper layer), and one or more intermediate layers existing therebetween. In this multilayer structure, the respective layers may contain different precious metals.
In the example illustrated in
The first catalyst body 20 can be manufactured in accordance with the known method. For example, a slurry containing a catalyst precious metal source, an OSC material, a non-OSC material, a solvent, and optional components is prepared. This slurry is applied to the second base material 70 in accordance with the known method and dried as necessary, which is then fired to form the first catalyst layer 40. Thus, the first catalyst body 20 can be obtained.
In the gasoline engine 1, the mixed gas with the air-fuel ratio from the rich region to the lean region including the theoretical air-fuel ratio is combusted. As illustrated in
The exhaust gas having flowed out of the upstream catalyst converter 10 flows into the downstream catalyst converter 50. Here, if the temperature inside the downstream catalyst converter 50 is so low that the temperature does not reach catalyst active temperature, NH3 cannot be purified. On the other hand, in the exhaust gas purifying system 100, the second catalyst body 60 includes the NH3 adsorption layer 80. Thus, NH3 included in the exhaust gas is adsorbed by the NH3 adsorption layer 80 included in the second catalyst body 60 of the downstream catalyst converter 50, and the emission out of the exhaust gas purifying system 100 is suppressed. NH3 adsorbed by the NH3 adsorption layer 80 is purified in the second catalyst layer 90 at a timing of, for example, fuel cutting (F/C).
Here, the exhaust gas purifying system is used in the high temperature environment, and the atmosphere varies between the rich atmosphere and the lean atmosphere in the gasoline engines, unlike in diesel engines and lean-burn engines. According to the present inventors' earnest examinations, it has been found out that if the atmosphere is in the rich to stoichiometric range under high temperature, oxygen becomes deficient and the structure of the zeolite used as the NH3 adsorber in the NH3 adsorption layer deteriorates, so that the NH3 purifying performance deteriorates.
Based on this finding, the second catalyst layer 90 including the OSC material is stacked on the NH3 adsorption layer 80 in the second catalyst body 60 of the downstream catalyst converter 50 of the exhaust gas purifying system 100 according to this embodiment. Accordingly, oxygen can be released from the OSC material such that oxygen will not be deficient in the atmosphere. Here, since the second catalyst layer 90 exists in the state of being stacked on the NH3 adsorption layer 80, the effect of relieving the atmosphere is particularly high. Therefore, it is possible to effectively suppress the structure deterioration of the zeolite due to oxygen deficiency under high temperature and drastically suppress the decrease in NH3 purifying performance after duration.
An exhaust gas purifying system 200 for a gasoline engine according to a second embodiment illustrated in
By such a structure, particulate matter (PM) in the exhaust gas can be captured by the GPF. Accordingly, by this structure, the exhaust gas purifying system for a gasoline engine having the high NH3 purifying performance after duration and the lower PM emission can be provided.
An exhaust gas purifying system 300 for a gasoline engine according to a third embodiment illustrated in
By such a structure, PM in the exhaust gas can be captured by the GPF. Accordingly, by this structure, the exhaust gas purifying system for a gasoline engine having the high NH3 purifying performance after duration and the lower PM emission can be provided.
An exhaust gas purifying system 400 for a gasoline engine according to a fourth embodiment illustrated in
In an exhaust gas purifying system 500 for a gasoline engine according to a fifth embodiment illustrated in
In an exhaust gas purifying system 600 for a gasoline engine according to a sixth embodiment illustrated in
In an exhaust gas purifying system 700 for a gasoline engine according to a seventh embodiment illustrated in
In an exhaust gas purifying system 800 for a gasoline engine according to an eighth embodiment illustrated in
The exhaust gas purifying system 100 for a gasoline engine can be used suitably for purifying the exhaust gas emitted from the gasoline engines of not only vehicles such as an automobile, a truck, and a motorcycle but also vessels and the like. Especially, the exhaust gas purifying system 100 for a gasoline engine can be used suitably for vehicles such as an automobile and a truck including a gasoline engine.
Test Examples about the present invention are hereinafter described but it is not intended to limit the present invention to Test Examples below.
As the first base material, a honeycomb base material (made of cordierite, diameter: 117 mm, overall length: 100 mm, and the number of cells per square inch: 600 cpsi) was prepared. A Pd-containing slurry was prepared by mixing palladium nitrate, CeO2—ZrO2-based composite oxide powder (OSC material), Al2O3 powder, barium sulfate, a binder, and ion exchange water. This Pd-containing slurry was poured into the first base material as a slurry for lower layer formation and an unnecessary part was blown away with a blower; thus, a surface of the first base material was coated with a material for lower layer formation. By firing this in an electric furnace, a lower layer containing a Pd catalyst was formed on the first base material.
A Rh-containing slurry was prepared by mixing rhodium nitrate, CeO2—ZrO2-based composite oxide powder (OSC material), Al2O3 powder, a binder, and ion exchange water. This Rh-containing slurry was poured into the first base material where the lower layer was formed, as a slurry for upper layer formation and an unnecessary part was blown away with the blower; thus, a surface of the lower layer formed on the base material was coated with a material for upper layer formation. By firing this in the electric furnace, an upper layer containing a Rh catalyst was formed on the lower layer. In this manner, the first catalyst body was manufactured.
Next, the same honeycomb base material as that of the first base material was prepared as the second base material. A zeolite-containing slurry was prepared by mixing a Cu-carrying CHA type zeolite (Cu—CHA), a binder, and ion exchange water. This zeolite-containing slurry was poured into the second base material as a slurry for lower layer formation and an unnecessary part was blown away with the blower; thus, a surface of the second base material was coated with a material for lower layer formation. By firing this in the electric furnace, a lower layer containing the zeolite was formed on the second base material.
The Pd-containing slurry, which was prepared above, was poured into the second base material where the lower layer was formed, as a slurry for intermediate layer formation and an unnecessary part was blown away with the blower; thus, a surface of the lower layer formed on the second base material was coated with a material for intermediate layer formation. By firing this in the electric furnace, an intermediate layer containing the Rh catalyst was formed on the lower layer.
The Rh-containing slurry, which was manufactured above, was poured into the second base material where the intermediate layer was formed, as a slurry for upper layer formation and an unnecessary part was blown away with the blower; thus, a surface of the intermediate layer formed over the second base material was coated with a material for upper layer formation. By firing this in the electric furnace, an upper layer containing the Rh catalyst was formed on the intermediate layer. In this manner, the second catalyst body was manufactured. By combining the first catalyst body and the second catalyst body that were manufactured, an exhaust gas purifying system according to Example 1 was constructed. A layer structure of the second catalyst body is schematically illustrated in
The first catalyst body was manufactured in a manner similar to Example 1. Next, a zeolite-containing slurry was prepared by mixing a Cu-carrying CHA type zeolite, CeO2—ZrO2-based composite oxide powder (OSC material), a binder, and ion exchange water. The second catalyst body was manufactured in a manner similar to Example 1 except that this zeolite-containing slurry was used as a slurry for lower layer formation and the amount of the OSC material in the Pd-containing slurry and the Rh-containing slurry was reduced so that the amount of the OSC material in the entire second catalyst body became the same as that of the second catalyst body in Example 1. By combining the first catalyst body and the second catalyst body that were manufactured, an exhaust gas purifying system according to Example 2 was constructed. A layer structure of the second catalyst body is schematically illustrated in
The first catalyst body was manufactured in a manner similar to Example 1. Next, a zeolite-containing slurry was prepared by mixing a Cu-carrying CHA type zeolite, palladium nitrate, CeO2—ZrO2-based composite oxide powder (OSC material), a binder, and ion exchange water. The second catalyst body was manufactured in a manner similar to Example 1 except that this zeolite-containing slurry was used as a slurry for lower layer formation, the amount of Pd in the Pd-containing slurry was reduced so that the amount of Pd in the entire second catalyst body became the same as that of the second catalyst body in Example 1, and the amount of the OSC material in the Pd-containing slurry and the Rh-containing slurry was reduced so that the amount of the OSC material in the entire second catalyst body became the same as that of the second catalyst body in Example 1. By combining the first catalyst body and the second catalyst body that were manufactured, an exhaust gas purifying system according to Example 3 was constructed. A layer structure of the second catalyst body is schematically illustrated in
The first catalyst body was manufactured in a manner similar to Example 1. The same second base material as that in Example 1 was prepared. The Pd-containing slurry, which was prepared in Example 1, was poured into the second base material as a slurry for lower layer formation and an unnecessary part was blown away with the blower; thus, the surface of the second base material was coated with a material for lower layer formation. By firing this in the electric furnace, a lower layer containing Pd was formed on the second base material.
The Rh-containing slurry, which was prepared in Example 1, was poured into the second base material where the lower layer was formed, as a slurry for intermediate layer formation and an unnecessary part was blown away with the blower; thus, a surface of the lower layer formed on the second base material was coated with a material for intermediate layer formation. By firing this in the electric furnace, an intermediate layer containing the Rh catalyst was formed on the lower layer.
The zeolite-containing slurry, which was prepared in Example 1, was poured into the second base material where the intermediate layer was formed, as a slurry for upper layer formation and an unnecessary part was blown away with the blower; thus, a surface of the intermediate layer formed over the second base material was coated with a material for upper layer formation. By firing this in the electric furnace, an upper layer containing the zeolite was formed on the intermediate layer. In this manner, the second catalyst body was manufactured. By combining the first catalyst body and the second catalyst body that were manufactured, an exhaust gas purifying system according to Example 4 was constructed. A layer structure of the second catalyst body is schematically illustrated in
The first catalyst body was manufactured in a manner similar to Example 1. The same second base material as that in Example 1 was prepared. The zeolite-containing slurry, which was prepared in Example 1, was poured up to a position corresponding to 50% of the overall length of the base material from the front part of the second base material and an unnecessary part was blown away with the blower; thus, a surface of the front part of the second base material was coated with a material for front part formation. By firing this in the electric furnace, a front layer containing the zeolite was formed in the front part of the base material.
The Pd-containing slurry, which was prepared in Example 1, was poured up to the position corresponding to 50% of the overall length of the base material from the rear part of the second base material and an unnecessary part was blown away with the blower; thus, a surface of the rear part of the second base material was coated with a material for rear part lower layer formation. By firing this in the electric furnace, a lower layer containing Pd was formed in the rear part of the second base material.
The Rh-containing slurry, which was prepared in Example 1, was poured up to the position corresponding to 50% of the overall length of the base material from the rear part of the second base material and an unnecessary part was blown away with the blower; thus, a surface of the lower layer of the rear part of the second base material was coated with a material for rear part upper layer formation. By firing this in the electric furnace, an upper layer containing Pd was formed on the lower layer in the rear part of the second base material. In this manner, the second catalyst body was manufactured. By combining the first catalyst body and the second catalyst body that were manufactured, an exhaust gas purifying system according to Comparative Example 1 was constructed. A layer structure of the second catalyst body is schematically illustrated in
The first catalyst body was manufactured in a manner similar to Example 1. The second catalyst body was manufactured by switching the front part and the rear part of the second catalyst body according to Comparative Example 1. By combining the first catalyst body and the second catalyst body that were manufactured, an exhaust gas purifying system according to Comparative Example 2 was constructed. A layer structure of the second catalyst body is schematically illustrated in
The exhaust gas purifying system according to each of Examples and Comparative Examples was attached to an exhaust system of a V type 8-cylinder gasoline engine. Here, the first catalyst body was disposed so as to exist on the upstream side in the flowing direction of the exhaust gas in the exhaust system. The temperature of the inflow gas was set to 950° C. and the exhaust gas with each of the rich atmosphere, the stoichiometric atmosphere, and the lean atmosphere was repeatedly supplied to the exhaust gas purifying system every predetermined time for 50 hours. Thus, the first catalyst body was subjected to a durability treatment of 1000° C. and the second catalyst body was subjected to the durability treatment of 700° C.
The exhaust gas purifying system according to each of Examples and Comparative Examples after the aforementioned durability treatment was mounted on a vehicle equipped with a gasoline engine. Here, the first catalyst body was accommodated in the housing and attached to the position of the startup catalyst, and the second catalyst body was accommodated in the housing and attached to the underfloor position. On the downstream side of the second catalyst body, an FT-IR spectrometer was attached. This vehicle was driven in accordance with the WLTC mode on a chassis dynamometer and the ammonium concentration contained in the exhaust gas was measured; thus, the NH3 emission was determined. The results are shown in
As indicated by the results in
The comparison of Example 1 to Example 3 indicates that the NH3 emission after duration was smaller in the case where the OSC material and the catalyst precious metal were not disposed in the NH3 adsorption layer than in the case where the OSC material and the catalyst precious metal were disposed in the NH3 adsorption layer. Moreover, the comparison of Example 1 and Example 4 indicates that the NH3 emission after duration was smaller in the case where the NH3 adsorption layer was disposed below the catalyst layer.
Although the embodiments of the present invention have been described above, each of the above-described embodiments is merely one example. The present invention can be carried out in other various modes. The present invention can be carried out based on the contents disclosed in this specification and technical common sense in the field. The techniques described in the scope of claims include those in which the specific embodiments exemplified above are variously modified and changed. For example, a part of the aforementioned embodiment can be replaced by another modified aspect, and the other modified aspect can be added to the aforementioned embodiment. Additionally, the technical feature may be omitted as appropriate unless such a feature is described as an essential element.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-163182 | Oct 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/035860 | 9/27/2022 | WO |
