Ultra-low NOx and cold-start exhaust gas treatment system

Abstract

To provide an exhaust gas treatment system for treating an exhaust gas stream discharged from an internal combustion engine.SOLUTION: The present exhaust gas treatment system comprises: (i) a first catalyst comprising a coating and a first substrate, in which the coating includes a vanadium oxide carried on a first oxidic carrier containing titanium; (ii) a hydrocarbon injection device for injecting a fluid containing hydrocarbons into an exhaust gas stream exiting an outlet end of the first catalyst described in (i); and (iii) a second catalyst comprising a coating and a second substrate, in which the coating includes palladium carried on a second oxidic carrier containing one or more of zirconium, silicon, aluminum and titanium.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to an exhaust gas treatment system for treating exhaust gas flow from an internal combustion engine, comprising a first vanadium-containing catalyst, a hydrocarbon injector, and a second catalyst; a method for producing the first vanadium-containing catalyst; and a method for treating exhaust gas from an internal combustion engine using the exhaust gas treatment system. [Background technology]

[0002] For example, it is known that systems equipped with closed-coupled SCRs (ccSCRs) are designed to meet ultra-low NOx and N2O emission requirements (such as CARBs). US2018 / 0258811A1 discloses an exhaust gas treatment system comprising a first catalytic reduction device having a coating (film) containing copper-activated zeolite (this first catalytic reduction device is the first active component in the exhaust gas treatment system) and a second catalytic reduction device comprising vanadium. US2017 / 0152780A1 also discloses an exhaust gas treatment system comprising a first catalytic reduction device, a particulate filter downstream of the first catalytic reduction device having at least partially a catalytic oxidation coating for capturing soot particles and oxidizing one or more types of nitrogen oxides, and a second catalytic reduction device downstream of the filter for reducing NOx.

[0003] The above-mentioned ccSCR (when based on Cu-zeolite SCR) may become sulfated over time due to SO3 generated from the engine and internal SO3 generated by the SCR, even though there is no oxidation catalyst upstream. As a result, over time, the ccSCR may not be able to perform enough DeNOx to meet ultra-low emission regulations. WO2018 / 224651A2 discloses an exhaust gas treatment system comprising a first catalyst (the first active component of the exhaust gas treatment system) comprising palladium and SCR components supported on an oxide material, and a second catalyst downstream comprising a zeolite material containing platinum group metals, one or more vanadium oxides, and one or more of copper and iron. However, in order to meet environmental requirements, it is necessary to realize an exhaust gas treatment system that prevents sulfation and improves DeNOx while keeping costs down. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] US2018 / 0258811A1 [Patent Document 2] US2017 / 0152780A1 [Patent Document 3] WO2018 / 224651A2 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, one objective of the present invention is to provide an exhaust gas treatment system that prevents sulfation, improves general robustness against chemical fouling and poisoning, exhibits improved DeNOx to meet environmental requirements, has a particularly fast DeNOx response under transient conditions, and is also cost-effective. [Effects of the Invention]

[0006] Remarkably, the exhaust gas treatment system according to the present invention prevents sulfation, improves general robustness against chemical fouling and poisoning, exhibits improved DeNOx to meet environmental requirements by having a fast DeNOx response, especially under transient conditions, and is also cost-effective. [Brief explanation of the drawing]

[0007] [Figure 1] The NOx conversion rates of the V-SCR catalyst in Reference Example 4 are shown at two different temperatures, namely 200°C and 250°C. The NOx conversion rates were measured under conditions of a space velocity of 50,000 / hr, NO concentration of 500 ppm, and NH3 concentration of 500 ppm. As is clear from this figure, the efficiency of the V-SCR catalyst improves with increasing temperature, and in particular, the DeNOx conversion rate increases from approximately 78% at 200°C to over 95% at 250°C. [Figure 2] The responsiveness of the catalyst in Reference Example 4 (V-SCR catalyst) and the catalyst in Reference Example 6 (Cu-SCR catalyst) is shown. DeNOx was measured at 210°C and a space velocity of 50,000 / hr. [Figure 3]This is a schematic diagram of an engine and the exhaust gas treatment system according to the present invention. More specifically, the exhaust gas treatment system comprises an SCR catalyst, i.e., a V-SCR catalyst, and Pd-DOC located downstream of the V-SCR catalyst. Furthermore, an HC injector is installed between the outlet end of the V-SCR catalyst and the inlet end of the Pd-DOC, and a first urea injector is installed upstream of the inlet end of the V-SCR catalyst. Furthermore, this system comprises one of a first ammonia oxidation catalyst, an SCR catalyst, and a DOC / SCR mixed catalyst, which is located downstream of the Pd-DOC. This system further comprises a second ammonia oxidation (AMOX) catalyst and optionally DOC at its outlet end. This system further comprises a catalytic soot filter (CSF) downstream of the second AMOX catalyst and upstream of the SCR catalyst. Furthermore, a second urea injector is installed between the CSF and the SCR catalyst. Finally, this system further comprises an SCR catalyst or an AMOX catalyst. [Figure 4] The temperatures at the inlet and outlet ends of the V-SCR catalyst in Comparative Example 1, and the temperature at the outlet end of the Pd-DOC in Comparative Example 1, are shown against time. [Figure 5] The temperatures at the inlet and outlet ends of the Pd-DOC in the system of Example 1 are shown against the time during the hydrocarbon injection event. The temperature of the upstream V-SCR is also shown. [Figure 6] The NOx conversion rates measured at the outlets of System 1 and System 2 under steady-state conditions at 215°C are shown. [Figure 7] This shows the NOx conversion rates at the outlet end of the various catalysts forming systems A, B, and C at 290°C (steady state). [Figure 8] This shows the nitrous oxide produced at the outlet ends of the various catalysts forming systems A, B, and C at 290°C (steady state). [Figure 9] This shows the NOx conversion rates at the outlet ends of various catalysts forming systems A, B, and C during the WHTC (transient state). [Figure 10]This shows the nitrous oxide generated at the outlet ends of the various catalysts forming systems A, B, and C during the WHTC (transient state). [Modes for carrying out the invention]

[0008] Therefore, the present invention relates to an exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system is (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises palladium supported on a second oxide carrier containing one or more of zirconium, silicon, aluminum, and titanium, the second catalyst. It is equipped with, Here, the first catalyst described in (i) is the first catalyst of an exhaust gas treatment system installed downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. In an exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Regarding exhaust gas treatment systems.

[0009] The outlet end of the first catalyst described in (i) is in fluid communication with the inlet end of the second catalyst described in (iii), and it is preferable that no catalyst for processing the exhaust gas flow leaving the first catalyst is located in the exhaust gas treatment system between the outlet end of the first catalyst described in (i) and the inlet end of the second catalyst described in (iii).

[0010] The first catalyst preferably contains a nitrogen oxide (NOx) reducing component.

[0011] The vanadium oxide contained in the first catalyst is preferably one or more of vanadium(V) oxide, vanadium(IV) oxide, and vanadium(III) oxide.

[0012] With respect to the coating of the first catalyst, it is preferable that it contains vanadium oxide in an amount in the range of 1.0 to 10% by weight, more preferably 2.0 to 8.0% by weight, and even more preferably 2.5 to 6.0% by weight, based on the mass of the first oxide support.

[0013] The first oxide support containing titanium preferably further contains one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. The first oxide support is even more preferably further containing tungsten and silicon. Alternatively, the first oxide support is even more preferably further containing antimony and silicon.

[0014] Therefore, preferably, the present invention relates to an exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system is (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, Here, the coating contains vanadium oxide in an amount ranging from 1.0 to 10% by mass, more preferably from 2.0 to 8.0% by mass, based on the mass of the first oxide support, and the first oxide support containing titanium further contains one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises palladium supported on a second oxide carrier containing one or more of zirconium, silicon, aluminum, and titanium, the second catalyst. It is equipped with, Here, the first catalyst described in (i) is the first catalyst of the exhaust gas treatment system located downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. Herein, the present invention relates to an exhaust gas treatment system in which the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst.

[0015] From the viewpoint of the present invention, it is preferable that 80 to 98% by mass, more preferably 85 to 95% by mass, of the first oxide support consists of titania. It is preferable that 2 to 10% by mass, more preferably 5 to 15% by mass, of the first oxide support consists of tungsten and silicon (calculated as WO3 and SiO2). Alternatively, it is preferable that 2 to 10% by mass, more preferably 5 to 15% by mass, of the first oxide support consists of antimony and silicon (calculated as Sb2O3 and SiO2).

[0016] The coating of the first catalyst is 1-10 g / in. 3 In the range of 2-7 g / in 3 The range is, more preferably 3 to 5.5 g / in 3 It is preferable to include the first oxide carrier in a loading amount (supported amount) within the range of [specify range].

[0017] The coating of the first catalyst preferably further comprises an oxide binder. The oxide binder is selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably from the group consisting of alumina, silica, and mixtures of two or more thereof, and even more preferably silica.

[0018] The coating of the first catalyst preferably contains an oxide binder, more preferably the oxide binder disclosed above, in an amount ranging from 0.5 to 10% by mass, more preferably from 2 to 8% by mass, and even more preferably from 3 to 6% by mass, based on the mass of the first oxide support.

[0019] The first catalyst preferably has a coating that includes a vanadium oxide supported on a first oxide support containing titanium, more preferably titania, wherein the first oxide support further contains tungsten and silicon, and the coating preferably further contains the oxide binder defined above.

[0020] In relation to the present invention, it is preferable that 95 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the first catalyst consist of vanadium oxide supported on a first oxide support containing titanium, more preferably titania, and more preferably the oxide binder defined above. Furthermore, it is even more preferable that the first oxide support further contains tungsten and silicon.

[0021] It is preferable that up to 0.001% by mass, more preferably 0 to 0.001% by mass, even more preferably 0 to 0.0001% by mass, and even more preferably 0 to 0.00001% by mass of the coating of the first catalyst consist of palladium, preferably palladium and rhodium, more preferably palladium, platinum and rhodium, and even more preferably platinum group metals.

[0022] Preferably, up to 0.1% by mass, more preferably 0-0.1% by mass, even more preferably 0-0.01% by mass, and more preferably 0-0.001% by mass of the coating of the first catalyst consists of a zeolite material, more preferably a molecular sieve.

[0023] The first base material preferably consists of one or more of cordierite, aluminum titanate, and silicon carbide, more preferably one or more of cordierite and silicon carbide, more preferably containing cordierite, and more preferably consisting of (the aforementioned).

[0024] The first substrate is preferably a wall-flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a cordierite flow-through substrate.

[0025] Alternatively, the first substrate may contain a metallic substance, more preferably consisting of a metallic substance, and the metallic substance may more preferably contain oxygen and one or more of iron, chromium, and aluminum, and more preferably consisting of (the aforementioned). The first substrate may be a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and even more preferably a metallic flow-through substrate.

[0026] The first catalyst is 1.5-12 g / in 3 A loading amount in the range of 2.5 to 8 g / in, including the coating, more preferably 2.5 to 8 g / in 3 The range is, more preferably 3.5 to 6 g / in 3 It is preferable to include the coating in the loading amount within this range.

[0027] The coating of the first catalyst preferably extends over 95-100%, more preferably 98-100%, and even more preferably 99-100% of the axial length of the first substrate.

[0028] The first catalyst described in (i) preferably consists of a coating and a first substrate.

[0029] Regarding the second catalyst described in (iii), the second oxide carrier included in the coating of the second catalyst contains one or more of zirconium and aluminum, and more preferably contains aluminum and optionally zirconium.

[0030] It is preferable that 90 to 100% by mass, more preferably 95 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass of the second oxide carrier in the coating of the second catalyst consists of aluminum, oxygen, and optionally zirconium.

[0031] It is more preferable that 60 to 95% by mass, more preferably 75 to 85% by mass of the second oxide carrier consists of alumina, and 5 to 40% by mass, more preferably 15 to 25% by mass of the second oxide carrier consists of zirconia.

[0032] (iii) The coating of the second catalyst described in (iii) is in the range of 0.25 to 5 g / in 3 and more preferably in the range of 0.5 to 5 g / in 3 and more preferably in the range of 0.75 to 4 g / in 3 and more preferably in the range of 1 to 2 g / in 3 and preferably contains the second oxide carrier at a loading amount within this range.

[0033] (iii) The coating of the second catalyst described in (iii) contains palladium in the range of 5 to 90 g / ft 3 and preferably in the range of 10 to 70 g / ft 3 and more preferably in the range of 30 to 60 g / ft 3 and preferably contains palladium in an amount within this range.

[0034] Regarding the second catalyst, it is preferable that palladium is the only platinum group metal present in the coating of the second catalyst described in (iii).

[0035] The second base material preferably consists of one or more of cordierite, aluminum titanate, and silicon carbide, more preferably one or more of cordierite and silicon carbide, more preferably containing cordierite, and more preferably consisting of (the aforementioned).

[0036] The second substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a cordierite flow-through substrate.

[0037] Alternatively, the second substrate may contain a metallic substance, more preferably consisting of a metallic substance, which may more preferably contain oxygen and one or more of iron, chromium, and aluminum, and more preferably consisting of (the aforementioned). The second substrate may be a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and even more preferably a metallic flow-through substrate.

[0038] The second catalyst described in (iii) preferably consists of a coating and a second substrate.

[0039] It is preferable that up to 0.1% by mass, more preferably 0-0.1% by mass, even more preferably 0-0.01% by mass, and even more preferably 0-0.001% by mass of the coating of the second catalyst consist of vanadium oxide.

[0040] (iii) The second catalyst described above preferably has a coating of palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, more preferably aluminum and zirconium.

[0041] It is preferable that 98 to 100% by mass, preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the second catalyst consist of palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, and more preferably aluminum and zirconium.

[0042] Therefore, preferably, the present invention relates to an exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system is (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, Here, the coating contains vanadium oxide in an amount ranging from 1.0 to 10% by mass, more preferably from 2.0 to 8.0% by mass, based on the mass of the first oxide support, and the first oxide support containing titanium further contains one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises palladium supported on a second oxide carrier containing one or more of aluminum and zirconium, wherein 98 to 100% by mass of the coating of the second catalyst consists of palladium supported on a second oxide carrier containing one or more of aluminum and zirconium. It is equipped with, Here, the first catalyst described in (i) is the first catalyst of the exhaust gas treatment system located downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. In an exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Regarding exhaust gas treatment systems.

[0043] It is preferable that up to 0.1% by mass, more preferably 0-0.1% by mass, even more preferably 0-0.01% by mass, and more preferably 0-0.001% by mass of the coating of the second catalyst consist of a zeolite material, more preferably a molecular sieve.

[0044] From the viewpoint of the present invention, according to the alternative, the coating of the second catalyst described in (iii) further comprises a zeolite material, wherein the zeolite material contains one or more of Cu and Fe.

[0045] The zeolite material included in the coating of the second catalyst preferably has skeletal AEI, GME, CHA, MFI, BEA, FAU, MOR, or a mixture of two or more thereof, more preferably has skeletal AEI, CHA, BEA, or a mixture of two or more thereof, more preferably has skeletal CHA or AEI, and more preferably has skeletal CHA.

[0046] It is preferable that the zeolite material included in the coating of the second catalyst contains copper, and the amount of copper contained in the zeolite material, calculated as CuO, is more preferably in the range of 0.5 to 10 mass%, more preferably in the range of 1 to 7 mass%, and even more preferably in the range of 2.5 to 6 mass%, based on the total mass of the zeolite material. The amount of iron in the zeolite material, calculated as Fe2O3, is more preferably in the range of 0 to 0.01 mass%, more preferably in the range of 0 to 0.001 mass%, and even more preferably in the range of 0 to 0.0001 mass%, based on the total mass of the zeolite material.

[0047] It is preferable that 95-100% by mass, more preferably 98-100% by mass, even more preferably 99-100% by mass, and more preferably 99.5-100% by mass of the skeletal structure of the zeolite material contained in the coating of the second catalyst consist of Si, Al, O, and H. In this case, the molar ratio of Si to Al in the skeletal structure (calculated as molar SiO2:Al2O3) is more preferably in the range of 2:1-50:1, more preferably in the range of 4:1-45:1, more preferably in the range of 10:1-40:1, and more preferably in the range of 15:1-35:1.

[0048] It is preferable that the zeolite material included in the coating of the second catalyst contains iron. In this case, the amount of iron contained in the zeolite material, calculated as Fe2O3, is more preferably in the range of 0.1 to 10.0 mass%, more preferably in the range of 1.0 to 7.0 mass%, and even more preferably in the range of 2.5 to 5.5 mass%, based on the total mass of the zeolite material. It is more preferable that 95 to 100 mass%, more preferably 98 to 100 mass%, even more preferably 99 to 100 mass%, and even more preferably 99.5 to 100 mass%, of the skeletal structure of the zeolite material consists of Si, Al, O, and H. In this case, the molar ratio of Si to Al in the skeletal structure (calculated as molar SiO2:Al2O3) is more preferably in the range of 2:1 to 50:1, more preferably in the range of 4:1 to 45:1, more preferably in the range of 10:1 to 40:1, and even more preferably in the range of 15:1 to 35:1.

[0049] The zeolite material included in the coating of the second catalyst, more preferably having a skeletal CHA, preferably has a mean crystallite size measured by scanning electron microscopy of at least 0.1 micrometers, more preferably in the range of 0.1 to 3.0 micrometers, more preferably in the range of 0.3 to 1.5 micrometers, and more preferably in the range of 0.4 to 1.0 micrometers.

[0050] The second catalyst coating is 0.2-8 g / in. 3 The range is, more preferably 0.5 to 6 g / in 3 In the range of 1 to 4 g / in, more preferably 1 to 4 g / in 3 The zeolite material is included in a loading amount within the range of (iii) and the coating of the second catalyst described in (iii) is 0.3 to 0.75 g / in 3 More preferably 0.4 to 0.6 g / in 3 It is preferable to include a second oxide carrier in a loading amount within the range of [specify range].

[0051] For a coating of a second catalyst containing a zeolite material, it is preferable that the coating further contains an oxide binder. The oxide binder is selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of alumina, zirconia, and mixtures of two or more thereof; and even more preferably, it is zirconia. It is more preferable that the coating of the second catalyst contains the oxide binder in an amount ranging from 0.5 to 10% by mass, preferably 2 to 8% by mass, and more preferably 3 to 6% by mass, based on the total mass of the zeolite material. It is preferable that 95 to 100% by mass, more preferably 98 to 100% by mass, even more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass of the coating of the second catalyst consist of a zeolite material containing one or more of palladium, Cu, and Fe supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, and even more preferably the oxide binder defined above.

[0052] From the perspective of the present invention, the second catalyst is 0.3 to 5 g / in 3 The coating is included in the loading amount within the range of 1-4 g / in 3 A range of 1.5 to 4.6 g / in 3 It is preferable to include the coating in the loading amount within this range.

[0053] The coating of the second catalyst preferably extends over 95-100%, more preferably 98-100%, and even more preferably 99-100% of the axial length of the second substrate.

[0054] The system of the present invention further, (iv) A third catalyst having an inlet end and an outlet end, and comprising a coating and a third substrate, wherein the third substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the third substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the third substrate, and the coating comprises a zeolite material containing one or more vanadium oxides and one or more of Cu and Fe. It is preferable to have the following: In this exhaust gas treatment system, it is preferable that the third catalyst described in (iv) is located downstream of the second catalyst described in (iii), and the inlet end of the third catalyst is located upstream of the outlet end of the third catalyst.

[0055] Therefore, preferably, the present invention relates to an exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system is (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises palladium supported on a second oxide carrier containing one or more of zirconium, silicon, aluminum, and titanium, (iv) A third catalyst having an inlet end and an outlet end, and comprising a coating and a third substrate, wherein the third substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the third substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the third substrate, and the coating comprises a zeolite material containing one or more vanadium oxides and one or more of Cu and Fe. Equipped with, Here, the first catalyst described in (i) is the first catalyst of the exhaust gas treatment system located downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. In an exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Herein, the present invention relates to an exhaust gas treatment system in which the third catalyst described in (iv) is located downstream of the second catalyst described in (iii), and the inlet end of the third catalyst is located upstream of the outlet end of the third catalyst.

[0056] From an aspect of the present invention, it is preferable that the outlet end of the second catalyst described in (iii) is in fluid communication with the inlet end of the third catalyst described in (iv), and that in this exhaust gas treatment system, there is no catalyst for treating the exhaust gas flow leaving the second catalyst between the outlet end of the second catalyst described in (iii) and the inlet end of the third catalyst described in (iv).

[0057] With respect to the third catalyst described in (iv), according to the first embodiment, it is preferable that the coating of the third catalyst according to (iv) includes a zeolite material containing one or more of Cu and Fe.

[0058] The zeolite material included in the coating of the third catalyst preferably has skeletal AEI, GME, CHA, MFI, BEA, FAU, MOR, or a mixture of two or more thereof, more preferably has skeletal AEI, CHA, BEA, or a mixture of two or more thereof, and more preferably has skeletal CHA or AEI. Furthermore, it is preferable that the zeolite material included in the coating of the third catalyst has skeletal CHA.

[0059] The zeolite material included in the coating of the third catalyst contains copper, and in this case, the amount of copper contained in the zeolite material, calculated as CuO, is preferably in the range of 0.5 to 10% by mass, more preferably 1 to 8% by mass, even more preferably 2 to 7% by mass, and even more preferably 3 to 6% by mass, based on the total mass of the zeolite material. Furthermore, the amount of iron in the zeolite material, calculated as Fe2O3, is preferably in the range of 0 to 0.01% by mass, more preferably 0 to 0.001% by mass, and even more preferably 0 to 0.0001% by mass, based on the total mass of the zeolite material.

[0060] In the third catalyst coating, 95 to 100% by mass, more preferably 98 to 100% by mass, even more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the skeletal structure of the zeolite material consist of Si, Al, O, and H. In this case, the molar ratio of Si to Al in the skeletal structure (calculated as molar SiO2:Al2O3) is preferably in the range of 2:1 to 50:1, more preferably 4:1 to 45:1, more preferably 10:1 to 40:1, and more preferably 15:1 to 35:1.

[0061] The zeolite material included in the coating of the third catalyst contains iron, and in this case, the amount of iron contained in the zeolite material, when calculated as Fe2O3, is preferably in the range of 0.1 to 10.0 mass%, more preferably in the range of 1.0 to 7.0 mass%, and even more preferably in the range of 2.5 to 5.5 mass%, based on the total mass of the zeolite material. Furthermore, 95 to 100 mass%, more preferably 98 to 100 mass%, even more preferably 99 to 100 mass%, and even more preferably 99.5 to 100 mass%, of the skeletal structure of the zeolite material consists of Si, Al, O, and H, and in this case, the molar ratio of Si:Al in the skeletal structure (calculated as molar SiO2:Al2O3) is preferably in the range of 2:1 to 50:1, more preferably in the range of 4:1 to 45:1, more preferably in the range of 10:1 to 40:1, and even more preferably in the range of 15:1 to 35:1.

[0062] The zeolite material included in the coating of the third catalyst, more preferably having a skeletal CHA, preferably has an average crystal grain size measured by scanning electron microscopy of at least 0.1 micrometers, more preferably in the range of 0.1 to 3.0 micrometers, more preferably in the range of 0.3 to 1.5 micrometers, and more preferably in the range of 0.4 to 1.0 micrometers.

[0063] The coating of the third catalyst is 0.5-8 g / in. 3 The range is, more preferably 0.75 to 5 g / in. 3The range, more preferably 1 to 3.5 g / in 3 It is more preferable to include zeolite material in a loading amount within the range of [specify range].

[0064] The coating of the third catalyst described in (iv) preferably further contains an oxide binder.

[0065] The oxide binder is selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably from the group consisting of alumina, zirconia, and mixtures of two or more thereof, and even more preferably zirconia.

[0066] The coating of the third catalyst more preferably contains the oxide binder in an amount ranging from 0.5 to 10% by mass, preferably 2 to 8% by mass, and more preferably 3 to 6% by mass, based on the total mass of the zeolite material. With respect to the third catalyst described in (iv) of the first embodiment, the coating comprises a zeolite material containing one or more of Cu and Fe, wherein the zeolite material has a skeletal AEI, GME, CHA, MFI, BEA, FAU, MOR or a mixture of two or more thereof, more preferably a skeletal AEI, CHA, BEA or a mixture of two or more thereof, more preferably a skeletal CHA or AEI, and even more preferably a skeletal CHA, and it is preferable that the coating further comprises an oxide binder.

[0067] It is preferable that up to 0.001% by mass, more preferably 0 to 0.001% by mass, even more preferably 0 to 0.0001% by mass, and even more preferably 0 to 0.00001% by mass of the coating of the third catalyst consist of palladium, platinum, and rhodium, preferably platinum group metals.

[0068] It is preferable that up to 0.1% by mass, more preferably 0-0.1% by mass, even more preferably 0-0.01% by mass, and even more preferably 0-0.001% by mass of the coating of the third catalyst consist of vanadium oxide.

[0069] It is preferable that 95 to 100% by mass, more preferably 98 to 100% by mass, even more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass of the coating of the third catalyst consist of a zeolite material containing one or more of Cu and Fe, and more preferably the oxide binder defined above.

[0070] From the viewpoint of the present invention, the coating of the second catalyst described in (iii) preferably comprises palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, preferably aluminum and optionally zirconium, and more preferably such palladium. Furthermore, the coating of the third catalyst described in (iv) preferably comprises a zeolite material containing one or more of Cu and Fe, and more preferably the oxide binder defined above.

[0071] Therefore, preferably, the present invention relates to an exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system is (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, Here, the coating contains vanadium oxide in an amount ranging from 1.0 to 10% by mass, more preferably from 2.0 to 8.0% by mass, based on the mass of the first oxide support, and the first oxide support containing titanium further contains one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises one or more of zirconium, silicon, aluminum, and titanium, preferably palladium supported on a second oxide support containing aluminum and any zirconium, (iv) A third catalyst having an inlet end and an outlet end, and comprising a coating and a third substrate, wherein the third substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the third substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the third substrate, and the coating comprises a zeolite material containing one or more of Cu and Fe, and more preferably an oxide binder as defined above, the third catalyst. Equipped with, Here, the first catalyst described in (i) is the first catalyst of the exhaust gas treatment system located downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. In an exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Herein, the present invention relates to an exhaust gas treatment system in which the third catalyst described in (iv) is located downstream of the second catalyst described in (iii), and the inlet end of the third catalyst is located upstream of the outlet end of the third catalyst according to the first embodiment.

[0072] With respect to the third coating described in (iv) of the second embodiment, the coating of the third catalyst preferably contains a vanadium oxide, in which case it is preferable that the vanadium oxide is one or more of vanadium(V) oxide, vanadium(IV) oxide, and vanadium(III) oxide.

[0073] Furthermore, it is more preferable that the vanadium is supported on a third oxide support, in which case the coating of the third catalyst contains the vanadium oxide in an amount more preferably in the range of 1.5 to 10% by mass, more preferably in the range of 2.5 to 8% by mass, and even more preferably in the range of 3 to 6% by mass, based on the mass of the third oxide support.

[0074] The third oxide support contains titanium, and in this case, it is preferable that the third oxide support further contains one or more of tungsten, silicon, zirconium, and antimony, preferably one or more of tungsten, silicon, and antimony. Furthermore, it is even more preferable that the third oxide support further contains tungsten and silicon, or that the third oxide support further contains antimony and silicon.

[0075] It is more preferable that 80-98% by mass, more preferably 85-95% by mass, of the third oxide support consists of titania. It is even more preferable that 2-10% by mass, more preferably 5-15% by mass, of the third oxide support consists of tungsten and silicon (calculated as WO3 and SiO2). Alternatively, it is even more preferable that 2-10% by mass, more preferably 5-15% by mass, of the third oxide support consists of antimony and silicon (calculated as Sb2O3 and SiO2).

[0076] The coating of the third catalyst is 1-10 g / in. 3 In the range of 2-7 g / in 3 The range is, more preferably 3 to 5.5 g / in 3 It is preferable to include a third oxide carrier in a loading amount within the range of [specify range].

[0077] With regard to the coating of a third catalyst containing vanadium oxide, it is preferable that the coating of the third catalyst further contains an oxide binder. The oxide binder is selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, and mixtures of two or more thereof, and even more preferably silica.

[0078] The coating preferably contains the oxide binder in an amount ranging from 0.5 to 10% by mass, preferably 2 to 8% by mass, and more preferably 3 to 6% by mass, based on the mass of the third oxide support. With respect to the third coating described in (iv) of the second embodiment, it is preferable that the coating of the third catalyst further contains a platinum group metal component, in which case it is preferable that the platinum group metal component is one or more of palladium, platinum and rhodium, more preferably one or more of palladium and platinum.

[0079] The platinum group metal components are preferably platinum and palladium. In this case, the mass ratio of platinum to palladium, Pt:Pd, calculated as elements of the platinum group metal, is more preferably in the range of 2:1 to 18:1, more preferably in the range of 5:1 to 15:1, and more preferably in the range of 8:1 to 12:1.

[0080] The coating of the third catalyst is 1-30 g / in. 3 The range is more preferably 2-15 g / in 3 The range is more preferably 5-12 g / in 3 It is preferable that the platinum group metal component be included in a loading amount within the range of [specified range].

[0081] The platinum group metal component is preferably supported on an oxide material, in which case the oxide material is more preferably one or more of alumina, silica, zirconia, and titania, more preferably one or more of alumina, silica, and zirconia, and more preferably one or more of alumina and silica, in which case the oxide material is more preferably alumina doped with zirconia. The coating of the third catalyst is 0.1 to 4 g / in 3 The range is, more preferably 0.2 to 2 g / in 3 A range of 0.5 to 1.5 g / in 3 It is more preferable to include an oxide material supporting platinum group metal components in a loading amount within the range of [specify range].

[0082] With respect to the third catalyst described in (iv) of the second embodiment, it is preferable that 95 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the third catalyst consist of a platinum group component, more preferably a platinum group component supported on the oxide material defined above, a vanadium oxide supported on the third oxide support, and more preferably an oxide binder defined above.

[0083] With respect to the third catalyst described in (iv) of the second embodiment, it is preferable that 95 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the third catalyst consist of a platinum group component, more preferably a platinum group component supported on the oxide material defined above, a zeolite material containing one or more of Cu and Fe, and more preferably an oxide binder defined above.

[0084] From the viewpoint of the present invention, the third catalyst described in (iv) preferably comprises one or more of cordierite, aluminum titanate, and silicon carbide, more preferably one or more of cordierite and silicon carbide, more preferably cordierite, and more preferably (the aforementioned).

[0085] The third substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a cordierite flow-through substrate. The third substrate can also be made of metal, similar to the first and second substrates described above.

[0086] The third catalyst is 0.75-10 g / in 3 In the range of 1 to 7 g / in, more preferably 1 to 7 g / in 3 A range of 1.5 to 5.5 g / in 3 It is preferable that the coating be included in a loading amount within the range of [specify range].

[0087] The coating of the third catalyst preferably extends over 95-100%, more preferably 98-100%, and even more preferably 99-100% of the axial length of the third substrate.

[0088] The third substrate of the third catalyst preferably has a substrate length in the range of 2.54 to 25.4 cm (1 to 10 inches), more preferably in the range of 3.81 to 17.78 cm (1.5 to 7 inches), and even more preferably in the range of 5.08 to 10.16 cm (2 to 4 inches).

[0089] The third substrate of the third catalyst preferably has a substrate width in the range of 10.16 to 43.18 cm (4 to 17 inches), more preferably in the range of 17.78 to 38.10 cm (7 to 15 inches), and even more preferably in the range of 22.86 to 30.48 cm (9 to 12 inches).

[0090] The third catalyst described in (iv) preferably consists of a coating and a third substrate.

[0091] The first substrate of the first catalyst preferably has a substrate length in the range of 2.54 to 25.4 cm (1 to 10 inches), more preferably in the range of 5.08 to 20.32 cm (2 to 8 inches), and even more preferably in the range of 7.62 to 15.24 cm (3 to 6 inches).

[0092] The first substrate of the first catalyst preferably has a substrate width in the range of 2.54 to 50.8 cm (1 to 20 inches), more preferably in the range of 12.7 to 43.18 cm (5 to 17 inches), and even more preferably in the range of 20.32 to 38.1 cm (8 to 15 inches).

[0093] The second substrate of the second catalyst preferably has a substrate length in the range of 2.54 to 25.4 cm (1 to 10 inches), more preferably in the range of 3.81 to 17.78 cm (1.5 to 7 inches), and even more preferably in the range of 5.08 to 10.16 cm (2 to 4 inches).

[0094] The second substrate of the second catalyst preferably has a substrate width in the range of 10.16 to 50.8 cm (4 to 20 inches), more preferably in the range of 17.78 to 43.18 cm (7 to 17 inches), and even more preferably in the range of 22.86 to 38.1 cm (9 to 15 inches).

[0095] From the viewpoint of the present invention, it is preferable that the system further comprises a fourth catalyst, in which case the fourth catalyst is preferably one or more of an ammonia oxidation catalyst, a catalyst-equipped soot filter, and a selective catalytic reduction catalyst.

[0096] The fourth catalyst is preferably an ammonia oxidation catalyst, in which case the fourth catalyst preferably has an inlet end and an outlet end and comprises a coating and a fourth substrate. The fourth substrate has an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the fourth substrate, and comprises a plurality of passages defined by an inner wall, where the interface between the passages and the inner wall is defined by the surface of the inner wall. The coating of the fourth catalyst is disposed on the surface of the inner wall of the fourth substrate, and the coating contains an ammonia oxidation component. In the exhaust gas treatment system, the fourth catalyst is located downstream of the third catalyst as described in (iv), and the inlet end of the fourth catalyst is located upstream of the outlet end of the fourth catalyst. The outlet end of the third catalyst as described in (iv) is in fluid communication with the inlet end of the fourth catalyst, and in the exhaust gas treatment system, there is no catalyst for treating the exhaust gas leaving the third catalyst between the outlet end of the third catalyst and the inlet end of the fourth catalyst.

[0097] The ammonia oxidation component of the fourth catalyst coating preferably includes a zeolite material containing a platinum group metal component, one or more vanadium oxides, and one or more of Cu and Fe, and more preferably includes a zeolite material containing a platinum group metal component and one or more of Cu and Fe.

[0098] The ammonia oxidation component of the fourth catalyst coating preferably comprises a platinum group metal component supported on an oxide support, more preferably one or more of palladium and platinum, and a zeolite material, more preferably a zeolite material having a skeletal CHA and containing Cu, and more preferably (as described above).

[0099] Therefore, preferably, the present invention relates to an exhaust gas treatment system for treating an exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system is (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, Here, the coating more preferably contains the vanadium oxide in an amount ranging from 1.0 to 10% by mass, more preferably from 2.0 to 8.0% by mass, based on the mass of the first oxide support, and the first oxide support containing titanium more preferably contains one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating consists of palladium supported on a second oxide carrier containing one or more of zirconium, silicon, aluminum, and titanium, (iv) A third catalyst having an inlet end and an outlet end, and comprising a coating and a third substrate, wherein the third substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the third substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the third substrate, and the coating comprises a zeolite material containing one or more of Cu and Fe. Equipped with, Here, the first catalyst described in (i) is the first catalyst of the exhaust gas treatment system located downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. In an exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Here, in the exhaust gas treatment system, the third catalyst described in (iv) is located downstream of the second catalyst described in (iii), and the inlet end of the third catalyst is located upstream of the outlet end of the third catalyst according to the first embodiment. Here, the system further comprises a fourth catalyst, wherein the fourth catalyst is one or more of an ammonia oxidation catalyst, a catalyst-equipped soot filter, and a selective catalytic reduction catalyst, more preferably an ammonia oxidation catalyst, wherein the fourth catalyst has an inlet end and an outlet end, and comprises a coating and a fourth substrate. Here, the fourth substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the fourth substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, and a coating of the fourth catalyst is disposed on the surface of the inner wall of the fourth substrate, and the coating contains an ammonia oxidizing component. Herein, the present invention relates to an exhaust gas treatment system in which a fourth catalyst is located downstream of the third catalyst described in (iv), the inlet end of the fourth catalyst is located upstream of the outlet end of the fourth catalyst, the outlet end of the third catalyst described in (iv) is in fluid communication with the inlet end of the fourth catalyst, and in the exhaust gas treatment system, no catalyst for treating the exhaust gas that has exited the third catalyst is located between the outlet end of the third catalyst and the inlet end of the fourth catalyst.

[0100] From the viewpoint of the present invention, the system of the present invention preferably further comprises a fifth catalyst. In this case, the fifth catalyst is one or more of an ammonia oxidation catalyst, a diesel oxidation catalyst, a catalytic soot filter, and a selective catalytic reduction catalyst, and more preferably a catalytic soot filter.

[0101] The fifth catalyst has an inlet end and an outlet end, and preferably has a coating provided on the fifth substrate, more preferably on the wall flow filter substrate. Here, in the exhaust gas treatment system, the fourth catalyst is located downstream of the third catalyst described in (iv), the inlet end of the fourth catalyst is located upstream of the outlet end of the fourth catalyst, the outlet end of the fourth catalyst is in fluid communication with the inlet end of the fifth catalyst, and no catalyst is placed between the outlet end of the fourth catalyst and the inlet end of the fifth catalyst to treat the exhaust gas that has left the fourth catalyst in the exhaust gas treatment system.

[0102] The system of the present invention preferably further comprises a sixth catalyst, in which case the sixth catalyst is preferably one or more of an ammonia oxidation catalyst, a catalyst-equipped soot filter, and a selective catalytic reduction catalyst, more preferably a selective catalytic reduction catalyst. The selective catalytic reduction catalyst comprises one or more vanadium oxides and a zeolite material containing one or more of Cu and Fe, and more preferably comprises a zeolite material containing one or more of Cu and Fe.

[0103] Preferably, the sixth catalyst has an inlet end and an outlet end and is provided with a coating on the sixth substrate, and in the exhaust gas treatment system, the sixth catalyst is located downstream of the fifth catalyst, the inlet end of the sixth catalyst is located upstream of the outlet end of the sixth catalyst, the outlet end of the fifth catalyst is in fluid communication with the inlet end of the sixth catalyst, and there is no catalyst provided between the outlet end of the fifth catalyst and the inlet end of the sixth catalyst for treating the exhaust gas that has left the fifth catalyst in the exhaust gas treatment system.

[0104] The system further comprises an injection device for injecting fluid into the exhaust gas flow discharged from the internal combustion engine, the injection device being installed upstream of the sixth catalyst and downstream of the fifth catalyst, and the fluid is more preferably an aqueous urea solution.

[0105] Instead of doing as described above, it is more preferable that the fifth catalyst is a diesel oxidation catalyst and the sixth catalyst is a catalytic soot filter.

[0106] The fifth catalyst has an inlet end and an outlet end, and more preferably has a coating provided on the fifth substrate, more preferably on the wall flow filter substrate. In this exhaust gas treatment system, the fifth catalyst is located downstream of the fourth catalyst, the inlet end of the fifth catalyst is located upstream of the outlet end of the fifth catalyst, the outlet end of the fourth catalyst is in fluid communication with the inlet end of the fifth catalyst, and no catalyst is located between the outlet end of the fourth catalyst and the inlet end of the fifth catalyst to treat the exhaust gas that has exited the fourth catalyst in the exhaust gas treatment system.

[0107] It is more preferable that the sixth catalyst has an inlet end and an outlet end and is provided with a coating on the sixth substrate, and in the exhaust gas treatment system, the sixth catalyst is located downstream of the fifth catalyst, the inlet end of the sixth catalyst is located upstream of the outlet end of the sixth catalyst, the outlet end of the fifth catalyst is in fluid communication with the inlet end of the sixth catalyst, and it is more preferable that no catalyst for treating the exhaust gas that has left the fifth catalyst in the exhaust gas treatment system is provided between the outlet end of the fifth catalyst and the inlet end of the sixth catalyst.

[0108] The system of the present invention further comprises an injection device for injecting a fluid into the exhaust gas flow discharged from an internal combustion engine, wherein the injection device is preferably located upstream of the first catalyst and downstream of the upstream end of the exhaust gas treatment system, and the fluid is more preferably an aqueous urea solution.

[0109] The system of the present invention further comprises an injection device for injecting a fluid into the exhaust gas flow discharged from an internal combustion engine, wherein the injection device(s) are preferably located upstream of a selective catalytic reduction catalyst, and the fluid is more preferably an aqueous urea solution.

[0110] It is preferable that no hydrocarbon injection device is located upstream of the first catalyst described in (i) and downstream of the upstream end of the exhaust gas treatment system.

[0111] The system of the present invention preferably comprises one or more of the first catalyst described in (i), the hydrocarbon injection device described in (ii), the second catalyst described in (iii), and more preferably the third catalyst described in (iv) as defined above, and even more preferably the fourth to sixth catalysts as defined above.

[0112] The present invention further relates to a method for producing a first catalyst for the exhaust gas treatment system of the present invention, (a) Prepare a mixture comprising water, a solution of vanadium oxide, and a first oxide material containing titanium. (b) The mixture obtained in (a) is placed on the surface of the inner wall of a first substrate to obtain a slurry-treated substrate, wherein the first substrate has an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the first substrate, and comprises a plurality of passages defined by the inner wall, wherein the interface between the passage and the inner wall is defined by the surface of the inner wall. (c) Optionally, dry the slurry-treated substrate obtained in (b) to obtain a substrate on which the coating is placed. (d)(b) The slurry-treated substrate obtained in (b), preferably the dried slurry-treated substrate obtained in (c), is fired to obtain a coated substrate. Includes, Also, optionally, (b') The mixture obtained in (a) is placed on the surface of the coating placed on the substrate obtained in (d). (c')Optionally, dry the slurry-treated substrate obtained in (b'). The slurry-treated substrate obtained in (d')(b'), or the dried slurry-treated substrate obtained in (c'), is fired. Includes, Herein, we describe a method for obtaining the first catalyst from (d) or (d').

[0113] (a) preferably includes the following configuration: (a.1) Prepare a mixture containing water and a first oxide support containing titanium. Here, the first oxide support further contains one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. (a.2) Add a solution of vanadium oxide, more preferably a solution of one or more of vanadium oxalate, ammonium vanadate, and vanadium oxide, to the mixture obtained in (a.1). (a.3) More preferably, a source of oxide binder is added. The source of oxide binder is one or more of colloidal silica, alumina, and zirconia, and more preferably colloidal silica.

[0114] (b) preferably includes distributing the mixture over 95-100%, more preferably 98-100%, and even more preferably 99-100% of the axial length of the substrate.

[0115] The arrangement of the mixture described in (b) is preferably carried out by spraying the mixture onto the substrate or by immersing the substrate in the mixture, and more preferably by immersing the substrate in the mixture.

[0116] The drying described in (c) is preferably carried out in a gas atmosphere at a temperature in the range of 90 to 200°C, more preferably 120 to 160°C.

[0117] The drying described in (c) is preferably carried out in a gas atmosphere for a time ranging from 5 to 300 minutes, more preferably from 20 to 60 minutes.

[0118] The dried slurry-treated substrate obtained in (c) preferably has a moisture content in the range of 0 to 30%, more preferably in the range of 5 to 25%, and even more preferably in the range of 15 to 20%.

[0119] The gaseous atmosphere preferably contains one or more of the following: air, dilute air, and oxygen; more preferably, one or more of these; more preferably, it contains air; more preferably, it is air.

[0120] The firing described in (d) is preferably carried out in a gas atmosphere at a temperature in the range of 300 to 600°C, more preferably in the range of 400 to 550°C.

[0121] The firing described in (d) is preferably carried out in a gas atmosphere for a duration of 5 to 120 minutes, more preferably 20 to 40 minutes.

[0122] The gaseous atmosphere preferably contains one or more of the following: air, dilute air, and oxygen; more preferably, one or more of these; more preferably, it contains air; more preferably, it is air.

[0123] (b') preferably involves arranging the mixture over 95-100%, more preferably 98-100%, and even more preferably 99-100% of the axial length of the substrate.

[0124] The arrangement of the mixture described in (b') is preferably carried out by spraying the mixture onto the substrate or by immersing the substrate in the mixture, and more preferably by immersing the substrate in the mixture.

[0125] The drying described in (c') is preferably carried out in a gas atmosphere having a temperature in the range of 90 to 200°C, more preferably in the range of 120 to 160°C.

[0126] The drying described in (c') is preferably carried out in a gas atmosphere for a duration ranging from 5 minutes to 300 minutes, more preferably from 20 minutes to 60 minutes.

[0127] The dried slurry-treated substrate obtained in (c') preferably has a moisture content in the range of 0 to 30%, more preferably in the range of 5 to 25%, and even more preferably in the range of 15 to 20%.

[0128] The gaseous atmosphere preferably contains one or more of the following: air, dilute air, and oxygen; more preferably, one or more of these; more preferably, it contains air; more preferably, it is air.

[0129] The firing described in (d') is preferably carried out in a gas atmosphere at a temperature in the range of 300 to 600°C, more preferably in the range of 400 to 550°C.

[0130] The firing described in (d') is preferably carried out in a gas atmosphere for a duration of 5 to 120 minutes, more preferably 20 to 40 minutes.

[0131] The gaseous atmosphere preferably contains one or more of the following: air, dilute air, and oxygen; more preferably, one or more of these; more preferably, it contains air; more preferably, it is air.

[0132] The above method preferably consists of (a), (b), (c), (d) and optionally (b'), (c'), and (d').

[0133] The present invention further relates to a catalyst for an exhaust gas treatment system of the present invention, more preferably to the first catalyst described in (i), which is obtained or can be obtained by the method of the present invention.

[0134] The present invention further relates to the use of the catalyst of the present invention for selective catalytic reduction of NOx.

[0135] The present invention further relates to the use of an exhaust gas treatment system according to the present invention for treating exhaust gas flow from an internal combustion engine, preferably a diesel engine.

[0136] The present invention further relates to a method for processing exhaust gas flow from an internal combustion engine, (1) Prepare an exhaust gas flow from an internal combustion engine, preferably a diesel engine, wherein the exhaust gas flow contains one or more of NOx, ammonia, nitric oxide, and hydrocarbons. (2) Pass the exhaust gas flow prepared in (1) through the exhaust gas system according to the present invention. Regarding methods for providing such a system.

[0137] The present invention will be described by the following series of embodiments and combinations of embodiments arising from the shown dependencies and backreferences. In particular, it should be noted that in terms such as "the system described in any one of Embodiments 1 to 4," any clause referring to a certain range of embodiments means that all embodiments within that range are explicitly disclosed to those skilled in the art, that is, the wording of this clause should be understood to those skilled in the art as synonymous with "the system described in any one of Embodiments 1, 2, 3, and 4." Furthermore, it should be explicitly stated that the following series of embodiments are not a set of claims in the patent claims that would determine the scope of protection, but rather represent a appropriately systematic descriptive portion of the general and preferred aspects of the present invention.

[0138] 1. An exhaust gas treatment system for treating the exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises palladium supported on a second oxide carrier containing one or more of zirconium, silicon, aluminum, and titanium, the second catalyst. It is equipped with, Here, the first catalyst described in (i) is a first catalyst of the exhaust gas treatment system located downstream of the upstream end of the exhaust gas treatment device, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. In an exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Exhaust gas treatment system.

[0139] 2. The system according to Embodiment 1, wherein the outlet end of the first catalyst described in (i) is in fluid communication with the inlet end of the second catalyst described in (iii), and no catalyst for processing the exhaust gas flow leaving the first catalyst is located in the exhaust gas treatment system between the outlet end of the first catalyst described in (i) and the inlet end of the second catalyst described in (iii).

[0140] 3. The system according to Embodiment 1 or 2, wherein the first catalyst comprises a nitrogen oxide (NOx) reducing component.

[0141] 4. A system according to any one of Embodiments 1 to 3, wherein the vanadium oxide contained in the first catalyst is one or more of vanadium(V) oxide, vanadium(IV) oxide, and vanadium(III) oxide.

[0142] 5. The system according to any one of Embodiments 1 to 4, wherein the coating of the first catalyst contains vanadium oxide in an amount in the range of 1.0 to 10% by mass, preferably in the range of 2.0 to 8.0% by mass, and more preferably in the range of 2.5 to 6.0% by mass, based on the mass of the first oxide support.

[0143] 6. The first oxide support containing titanium further contains one or more of tungsten, silicon, zirconium, and antimony, preferably one or more of tungsten, silicon, and antimony. The system according to any one of Embodiments 1 to 5, wherein the first oxide support preferably further comprises tungsten and silicon, or the first oxide support preferably further comprises antimony and silicon.

[0144] 7. The system according to any one of Embodiments 1 to 6, wherein 80 to 98% by mass, more preferably 85 to 95% by mass of the first oxide support consists of titania, and where preferably 2 to 10% by mass, more preferably 5 to 15% by mass of the first oxide support consists of tungsten and silicon, or antimony and silicon (calculated as WO3 and SiO2, or Sb2O3 and SiO2, respectively).

[0145] 8. The coating of the first catalyst is 1-10 g / in 3 In the range of 2-7 g / in 3 The range is, more preferably 3 to 5.5 g / in 3 A system according to any one of embodiments 1 to 7, comprising a first oxide carrier in a loading amount within the range of .

[0146] 9. The coating of the first catalyst further comprises an oxide binder, the oxide binder preferably selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, and mixtures of two or more thereof, and more preferably silica. The system according to any one of Embodiments 1 to 8, wherein the coating of the first catalyst contains an oxide binder in an amount ranging from 0.5 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 3 to 6% by mass, based on the mass of the first oxide support.

[0147] 10. A system according to any one of Embodiments 1 to 9, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the first catalyst is vanadium oxide supported on a first oxide support containing titanium, preferably titania, wherein the first oxide support more preferably further contains tungsten and silicon, and preferably comprises an oxide binder as defined in Embodiment 9.

[0148] 11. The system according to any one of Embodiments 1 to 10, wherein up to 0.001% by mass, more preferably 0 to 0.001% by mass, even more preferably 0 to 0.0001% by mass, and even more preferably 0 to 0.00001% by mass of the coating of the first catalyst is made of palladium, preferably palladium and rhodium, more preferably palladium, platinum and rhodium, and even more preferably platinum group metals.

[0149] 12. The system according to any one of Embodiments 1 to 11, wherein up to 0.1% by mass, preferably 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, and more preferably 0 to 0.001% by mass of the coating of the first catalyst consists of a zeolite material, preferably a molecular sieve.

[0150] 13. The first base material consists of one or more of cordierite, aluminum titanate, and silicon carbide, preferably consisting of one or more of cordierite and silicon carbide, and more preferably consisting of cordierite. The first substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a cordierite flow-through substrate. The first base material contains a metallic substance, preferably consisting of a metallic substance, which preferably contains oxygen and one or more of iron, chromium, and aluminum, and more preferably consisting of (those mentioned above). The system according to any one of Embodiments 1 to 12, wherein the first substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a metal flow-through substrate.

[0151] 14. The first catalyst is 1.5~12 g / in 3 The range is preferably 2.5 to 8 g / in. 3 The range is, more preferably 3.5 to 6 g / in 3 Including coatings within the range of loading amounts, The system according to any one of embodiments 1 to 13, wherein the coating of the first catalyst extends over 95 to 100%, more preferably 98 to 100%, and even more preferably 99 to 100% of the axial length of the first substrate.

[0152] The system according to any one of Embodiments 1 to 14, wherein the first catalyst described in 15.(i) comprises a coating and a first substrate.

[0153] The second oxide support included in the coating of the second catalyst described in 16.(iii) comprises one or more of zirconium and aluminum, preferably aluminum, and optionally zirconium. More preferably, 90-100% by mass, 95-100% by mass, 98-100% by mass, and 99-100% by mass of the second oxide support consist of aluminum, oxygen, and optionally zirconium. The system according to any one of Embodiments 1 to 15, wherein the second oxide support is more preferably composed of alumina in an amount of 60 to 95% by mass, more preferably 75 to 85% by mass, and the second oxide support is more preferably composed of zirconia in an amount of 5 to 40% by mass, more preferably 15 to 25% by mass.

[0154] The coating of the second catalyst described in 17.(iii) is 0.25-5 g / in 3 The range is, more preferably 0.5 to 5 g / in 3 The range is, more preferably 0.75 to 4 g / in. 3 In the range of 1-2 g / in, more preferably 1-2 g / in 3 A system according to any one of embodiments 1 to 16, comprising a second oxide carrier in a loading amount within the range of .

[0155] The coating of the second catalyst described in 18.(iii) is 5-90 g / ft 3 A range of preferably 10-70 g / ft 3 A comfortable range is 30-60 g / ft 3 A system according to any one of embodiments 1 to 17, comprising palladium in an amount within the range of .

[0156] 19. The system according to any one of Embodiments 1 to 18, wherein palladium is the only platinum group metal present in the coating of the second catalyst described in (iii).

[0157] 20. The second base material comprises one or more of cordierite, aluminum titanate, and silicon carbide, preferably one or more of cordierite and silicon carbide, more preferably cordierite (preferably consisting of), The second substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, more preferably a cordierite flow-through substrate; or The second base material contains a metallic substance, preferably consisting of a metallic substance, and the metallic substance preferably contains (more preferably consists of) oxygen and one or more of iron, chromium, and aluminum. The system according to any one of Embodiments 1 to 19, wherein the second substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a metal flow-through substrate.

[0158] The system according to any one of Embodiments 1 to 20, wherein the second catalyst described in 21.(iii) comprises a coating and a second substrate.

[0159] 22. The system according to any one of Embodiments 1 to 21, wherein up to 0.1% by mass, preferably 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, and more preferably 0 to 0.001% by mass of the coating of the second catalyst is made of vanadium oxide.

[0160] 23. The system according to any one of Embodiments 1 to 22, wherein 98 to 100% by mass, preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the second catalyst consists of palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, preferably aluminum and zirconium.

[0161] The system according to any one of Embodiments 1 to 22, wherein the coating of the second catalyst described in 24.(iii) further comprises a zeolite material, the zeolite material containing one or more of Cu and Fe.

[0162] 25. The system according to Embodiment 24, wherein the zeolite material included in the coating of the second catalyst has skeletal AEI, GME, CHA, MFI, BEA, FAU, MOR, or a mixture of two or more thereof, preferably having skeletal AEI, CHA, BEA, or a mixture of two or more thereof, more preferably having skeletal CHA or AEI, and more preferably having skeletal CHA.

[0163] 26. The zeolite material contained in the coating of the second catalyst contains copper, and the amount of copper contained in the zeolite material, when calculated as CuO, is more preferably in the range of 0.5 to 10% by mass, more preferably in the range of 1 to 7% by mass, and even more preferably in the range of 2.5 to 6% by mass, based on the total mass of the zeolite material. The system according to Embodiment 24 or 25, wherein the amount of iron in the zeolite material, when calculated as Fe2O3, is more preferably in the range of 0 to 0.01% by mass, more preferably 0 to 0.001% by mass, and even more preferably 0 to 0.0001% by mass, based on the total mass of the zeolite material.

[0164] 27. The system according to any one of embodiments 24 to 26, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the skeletal structure of the zeolite material contained in the coating of the second catalyst consists of Si, Al, O, and H, and the molar ratio of Si:Al in the skeletal structure (calculated as molar SiO2:Al2O3) is preferably in the range of 2:1 to 50:1, more preferably in the range of 4:1 to 45:1, more preferably in the range of 10:1 to 40:1, and more preferably in the range of 15:1 to 35:1.

[0165] 28. The system according to Embodiment 24 or 25, wherein the zeolite material included in the coating of the second catalyst contains iron, and the amount of iron in the zeolite material, calculated as Fe2O3, is preferably in the range of 0.1 to 10.0 mass%, more preferably in the range of 1.0 to 7.0 mass%, and even more preferably in the range of 2.5 to 5.5 mass%, based on the total mass of the zeolite material, and preferably 95 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, and even more preferably 99.5 to 100 mass%, of the skeletal structure of the zeolite material consists of Si, Al, O, and H, and the molar ratio of Si to Al in the skeletal structure, calculated as molar SiO2:Al2O3, is preferably in the range of 2:1 to 50:1, more preferably in the range of 4:1 to 45:1, more preferably in the range of 10:1 to 40:1, and even more preferably in the range of 15:1 to 35:1.

[0166] 29. The system according to any one of Embodiments 24 to 28, wherein the zeolite material included in the coating of the second catalyst, preferably the zeolite material having a skeletal CHA, has a mean crystallite size measured by scanning electron microscopy of at least 0.1 micrometers, preferably in the range of 0.1 to 3.0 micrometers, more preferably in the range of 0.3 to 1.5 micrometers, and more preferably in the range of 0.4 to 1.0 micrometers.

[0167] 30. The coating of the second catalyst should be 0.2-8 g / in. 3 The range is, more preferably 0.5 to 6 g / in 3 In the range of 1 to 4 g / in, more preferably 1 to 4 g / in 3 The zeolite material is included in a loading amount within the range of (iii) and the coating of the second catalyst described in (iii) is 0.3 to 0.75 g / in 3 More preferably 0.4 to 0.6 g / in 3 A system according to any one of embodiments 24 to 29, comprising a second oxide carrier in a loading amount within the range of .

[0168] The coating of the second catalyst described in 31.(iv) further comprises an oxide binder, wherein the oxide binder is preferably selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, and mixtures of two or more thereof, and more preferably zirconia. The system according to any one of embodiments 24 to 30, wherein the coating of the second catalyst preferably contains the oxide binder in an amount ranging from 0.5 to 10% by mass, preferably from 2 to 8% by mass, and more preferably from 3 to 6% by mass, based on the total mass of the zeolite material.

[0169] 32. The system according to any one of embodiments 24 to 31, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the second catalyst is a zeolite material containing one or more of palladium, Cu, and Fe supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, and preferably an oxide binder as defined in embodiment 31.

[0170] 33. The second catalyst is 0.3-5 g / in 3 In the range of 1-4 g / in 3 The range, more preferably 1.5 to 4.6 g / in 3 Including coatings within the range of loading amounts, The system according to any one of embodiments 1 to 32, wherein the coating of the second catalyst extends over 95 to 100%, more preferably 98 to 100%, and even more preferably 99 to 100% of the axial length of the second substrate.

[0171] 34. Furthermore, (iv) A third catalyst having an inlet end and an outlet end, and comprising a coating and a third substrate, wherein the third substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the third substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the third substrate, and the coating comprises a zeolite material containing one or more vanadium oxides and one or more of Cu and Fe. Equipped with, Herein, in the exhaust gas treatment system, the system according to any one of Embodiments 1 to 33, wherein the third catalyst described in (iv) is located downstream of the second catalyst described in (iii), and the inlet end of the third catalyst is located upstream of the outlet end of the third catalyst.

[0172] The system according to Embodiment 34, wherein the outlet end of the second catalyst described in (iii) is in fluid communication with the inlet end of the third catalyst described in (iv), and no catalyst for processing the exhaust gas flow leaving the second catalyst is located in the exhaust gas treatment system between the outlet end of the second catalyst described in (iii) and the inlet end of the third catalyst described in (iv).

[0173] The system according to Embodiment 34 or 35, wherein the coating of the third catalyst described in 36.(iv) includes a zeolite material containing one or more of Cu and Fe.

[0174] 37. The system according to Embodiment 36, wherein the zeolite material included in the coating of the third catalyst has skeletal AEI, GME, CHA, MFI, BEA, FAU, MOR, or a mixture of two or more thereof, preferably having skeletal AEI, CHA, BEA, or a mixture of two or more thereof, more preferably having skeletal CHA or AEI, and more preferably having skeletal CHA.

[0175] 38. The zeolite material included in the coating of the third catalyst contains copper, and in this case, the amount of copper included in the zeolite material is calculated as CuO and is preferably in the range of 0.5 to 10% by mass, more preferably 1 to 8% by mass, even more preferably 2 to 7% by mass, and even more preferably 3 to 6% by mass, based on the total mass of the zeolite material. The system according to Embodiment 36 or 37, wherein the amount of iron in the zeolite material, when calculated as Fe2O3, is more preferably in the range of 0 to 0.01% by mass, more preferably 0 to 0.001% by mass, and even more preferably 0 to 0.0001% by mass, based on the total mass of the zeolite material.

[0176] 39. The system according to any one of embodiments 36 to 38, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the skeletal structure of the zeolite material contained in the coating of the third catalyst consists of Si, Al, O, and H, and the molar ratio of Si:Al in the skeletal structure (calculated as molar SiO2:Al2O3) is preferably in the range of 2:1 to 50:1, more preferably in the range of 4:1 to 45:1, more preferably in the range of 10:1 to 40:1, and more preferably in the range of 15:1 to 35:1.

[0177] 40. The system according to Embodiment 36 or 37, wherein the zeolite material included in the coating of the third catalyst contains iron, and the amount of iron in the zeolite material, calculated as Fe2O3, is preferably in the range of 0.1 to 10.0 mass%, more preferably in the range of 1.0 to 7.0 mass%, and even more preferably in the range of 2.5 to 5.5 mass%, based on the total mass of the zeolite material, and preferably 95 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, and even more preferably 99.5 to 100 mass%, of the skeletal structure of the zeolite material consists of Si, Al, O, and H, and the molar ratio of Si to Al in the skeletal structure, calculated as molar SiO2:Al2O3, is preferably in the range of 2:1 to 50:1, more preferably in the range of 4:1 to 45:1, more preferably in the range of 10:1 to 40:1, and even more preferably in the range of 15:1 to 35:1.

[0178] 41. The system according to any one of Embodiments 36 to 40, wherein the zeolite material included in the coating of the third catalyst, preferably having a skeletal CHA, has an average crystal grain size measured by scanning electron microscopy of at least 0.1 micrometers, preferably in the range of 0.1 to 3.0 micrometers, more preferably in the range of 0.3 to 1.5 micrometers, and more preferably in the range of 0.4 to 1.0 micrometers.

[0179] 42. The coating of the third catalyst is 0.5~8 g / in 3The range is preferably 0.75 to 5 g / in. 3 The range is, more preferably 1 to 3.5 g / in 3 A system according to any one of embodiments 36 to 41, comprising zeolite material in a loading amount within the range of [specify range].

[0180] The system according to any one of Embodiments 36 to 42, wherein the coating of the third catalyst described in 43.(iv) further comprises an oxide binder, wherein the oxide binder is preferably selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, zirconia, and mixtures of two or more thereof, and more preferably zirconia.

[0181] 44. The system according to Embodiment 42, wherein the coating of the third catalyst contains the oxide binder in an amount ranging from 0.5 to 10% by mass, preferably 2 to 8% by mass, and more preferably 3 to 6% by mass, based on the total mass of the zeolite material.

[0182] 45. The system according to any one of embodiments 36 to 44, wherein up to 0.001% by mass, preferably 0 to 0.001% by mass, more preferably 0 to 0.0001% by mass, and even more preferably 0 to 0.00001% by mass of the coating of the third catalyst consists of palladium, platinum, and rhodium, preferably platinum group metals.

[0183] 46. ​​The system according to any one of embodiments 36 to 45, wherein up to 0.1% by mass, preferably 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, and more preferably 0 to 0.001% by mass of the coating of the third catalyst is made of vanadium oxide.

[0184] 47. A system according to any one of Embodiments 36 to 46, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the third catalyst consists of a zeolite material containing one or more of Cu and Fe, and preferably an oxide binder as described in Embodiment 43 or 44.

[0185] The coating of the second catalyst described in 48.(iii) comprises palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, preferably aluminum and optionally zirconium (preferably consisting of), wherein the coating of the third catalyst described in (iv) comprises a zeolite material containing one or more of Cu and Fe, and preferably the oxide binder described in Embodiment 43 or 44 (preferably consisting of), the system described in any one of Embodiments 36 to 47.

[0186] 49. The system according to Embodiment 34 or 35, wherein the coating of the third catalyst contains a vanadium oxide, and the vanadium oxide is one or more of vanadium(V) oxide, vanadium(IV) oxide, and vanadium(III) oxide.

[0187] 50. The system according to Embodiment 49, wherein the vanadium is supported on a third oxide support, and the coating of the third catalyst contains the vanadium oxide in an amount preferably in the range of 1.5 to 10% by mass, more preferably in the range of 2.5 to 8% by mass, and even more preferably in the range of 3 to 6% by mass, based on the mass of the third oxide support.

[0188] 51. The system according to Embodiment 49 or 50, wherein the third oxide support comprises titanium, and the third oxide support further comprises one or more of tungsten, silicon, zirconium, and antimony, preferably one or more of tungsten, silicon, and antimony.

[0189] 52. The system according to Embodiment 51, wherein the third oxide support further comprises tungsten and silicon, or the third oxide support further comprises antimony and silicon.

[0190] 53. The system according to any one of embodiments 50 to 52, wherein 80 to 98% by mass, more preferably 85 to 95% by mass of the third oxide support is titania, and 2 to 10% by mass, more preferably 5 to 15% by mass of the third oxide support is tungsten and silicon, or antimony and silicon (calculated as WO3 and SiO2, or Sb2O3 and SiO2, respectively).

[0191] 54. The coating of the third catalyst is 1-10 g / in 3 In the range of 2-7 g / in 3 The range is, more preferably 3 to 5.5 g / in 3 The system according to any one of embodiments 50 to 53, comprising a third oxide carrier in a loading amount within the range of .

[0192] 55. The coating of the third catalyst further comprises an oxide binder, the oxide binder preferably selected from the group consisting of alumina, silica, zirconia, and mixtures of two or more thereof, more preferably selected from the group consisting of alumina, silica, and mixtures of two or more thereof, and more preferably silica. The system according to any one of embodiments 50 to 54, wherein the coating contains an amount of the oxide binder in the range of 0.5 to 10% by mass, preferably in the range of 2 to 8% by mass, and more preferably in the range of 3 to 6% by mass, based on the mass of the third oxide support.

[0193] 56. The system according to any one of embodiments 36 to 44 and 49 to 55, wherein the coating of the third catalyst further comprises a platinum group metal component, the platinum group metal component being one or more of palladium, platinum, and rhodium, preferably one or more of palladium and platinum.

[0194] 57. The system according to Embodiment 56, wherein the platinum group metal components are platinum and palladium, and the mass ratio of platinum to palladium, Pt:Pd, calculated as elemental platinum group metals, is preferably in the range of 2:1 to 18:1, more preferably in the range of 5:1 to 15:1, and more preferably in the range of 8:1 to 12:1.

[0195] 58. The coating of the third catalyst is 1-30 g / in 3 The range is more preferably 2-15 g / in 3 The range is more preferably 5-12 g / in 3 The system according to embodiment 56 or 57, comprising the platinum group metal component in a loading amount within the range of [amount].

[0196] 59. The system according to any one of embodiments 56 to 58, wherein the platinum group metal component is supported on an oxide material, the oxide material is preferably one or more of alumina, silica, zirconia, and titania, more preferably one or more of alumina, silica, and zirconia, and more preferably one or more of alumina and silica, and the oxide material is more preferably alumina doped with zirconia.

[0197] 60. The coating of the third catalyst is 0.1~4 g / in 3 The range is, more preferably 0.2 to 2 g / in 3 A range of 0.5 to 1.5 g / in 3 The system according to Embodiment 59, comprising an oxide material supporting a platinum group metal component in a loading amount within the range of [amount].

[0198] 61. The system according to any one of embodiments 56 to 60, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the third catalyst consists of a platinum group component, preferably a platinum group component supported on an oxide material as defined in Embodiment 59 or 60, a vanadium oxide supported on a third oxide support, and preferably an oxide binder as defined in Embodiment 55.

[0199] 62. The system according to any one of embodiments 56 to 60, wherein 95 to 100% by mass, preferably 98 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass of the coating of the third catalyst comprises a platinum group component, preferably a platinum group component supported on an oxidizing material as defined in Embodiment 59 or 60, a zeolite material containing one or more of Cu and Fe, and preferably an oxide binder as described in Embodiment 43 or 44.

[0200] 63. The third base material comprises one or more of cordierite, aluminum titanate, and silicon carbide, preferably one or more of cordierite and silicon carbide, more preferably cordierite, The system according to any one of embodiments 34 to 62, wherein the third substrate is preferably a wall flow filter substrate or a flow-through substrate, more preferably a flow-through substrate, and more preferably a cordierite flow-through substrate.

[0201] 64. The third catalyst is 0.75~10 g / in 3 In the range of 1 to 7 g / in 3 The range, more preferably 1.5 to 5.5 g / in 3 Including coatings within the range of loading amounts, The system according to any one of embodiments 34 to 63, wherein the coating of the third catalyst extends over 95 to 100%, more preferably 98 to 100%, and even more preferably 99 to 100% of the axial length of the third substrate.

[0202] 65. The system according to any one of embodiments 34 to 64, wherein the third substrate of the third catalyst has a substrate length in the range of 2.54 to 25.4 cm (1 to 10 inches), preferably in the range of 3.81 to 17.78 cm (1.5 to 7 inches), and more preferably in the range of 5.08 to 10.16 cm (2 to 4 inches).

[0203] 66. The system according to any one of embodiments 34 to 65, wherein the third substrate of the third catalyst has a substrate width in the range of 10.16 to 43.18 cm (4 to 17 inches), preferably in the range of 17.78 to 38.10 cm (7 to 15 inches), and more preferably in the range of 22.86 to 30.48 cm (9 to 12 inches).

[0204] The system according to any one of embodiments 34 to 66, wherein the third catalyst described in 67.(iv) comprises a coating and a third substrate.

[0205] 68. The system according to any one of Embodiments 1 to 67, wherein the first substrate of the first catalyst has a substrate length in the range of 2.54 to 25.4 cm (1 to 10 inches), preferably in the range of 5.08 to 20.32 cm (2 to 8 inches), and more preferably in the range of 7.62 to 15.24 cm (3 to 6 inches).

[0206] 69. The system according to any one of Embodiments 1 to 68, wherein the first substrate of the first catalyst has a substrate width in the range of 2.54 to 50.8 cm (1 to 20 inches), preferably in the range of 12.7 to 43.18 cm (5 to 17 inches), and more preferably in the range of 20.32 to 38.1 cm (8 to 15 inches).

[0207] 70. The system according to any one of embodiments 34 to 64, wherein the second substrate of the second catalyst has a substrate length in the range of 2.54 to 25.4 cm (1 to 10 inches), preferably in the range of 3.81 to 17.78 cm (1.5 to 7 inches), and more preferably in the range of 5.08 to 10.16 cm (2 to 4 inches).

[0208] 71. The system according to any one of embodiments 34 to 65, wherein the second substrate of the second catalyst has a substrate width in the range of 10.16 to 50.8 cm (4 to 20 inches), preferably in the range of 17.78 to 43.18 cm (7 to 17 inches), and more preferably in the range of 22.86 to 38.1 cm (9 to 15 inches).

[0209] 72. The system according to any one of embodiments 34 to 71, further comprising a fourth catalyst, the fourth catalyst being one or more of an ammonia oxidation catalyst, a catalytic soot filter, and a selective catalytic reduction catalyst.

[0210] 73. The fourth catalyst is an ammonia oxidation catalyst, the fourth catalyst having an inlet end and an outlet end, and comprising a coating and a fourth substrate, the fourth substrate having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the fourth substrate, comprising a plurality of passages defined by an inner wall, the interface between the passages and the inner wall being defined by the surface of the inner wall, the coating being disposed on the surface of the inner wall of the fourth substrate, and the coating containing an ammonia oxidation component. In an exhaust gas treatment system, the fourth catalyst is located downstream of the third catalyst described in (iv), and the inlet end of the fourth catalyst is located upstream of the outlet end of the fourth catalyst. The system according to Embodiment 72, wherein the outlet end of the third catalyst described in (iv) is in fluid communication with the inlet end of the fourth catalyst, and in the exhaust gas treatment system, no catalyst for treating the exhaust gas leaving the third catalyst is placed between the outlet end of the third catalyst and the inlet end of the fourth catalyst.

[0211] 74. The system according to Embodiment 73, wherein the ammonia oxidation component of the coating of the fourth catalyst comprises a zeolite material containing a platinum group metal component, one or more vanadium oxides, and one or more of Cu and Fe, preferably a zeolite material containing a platinum group metal component and one or more of Cu and Fe.

[0212] 75. The system according to Embodiment 74, wherein the ammonia oxidation component of the fourth catalyst coating comprises a platinum group metal component supported on an oxide support, preferably one or more of palladium and platinum, and Cu, preferably a zeolite material having a skeletal CHA, preferably (as described above).

[0213] 76. Further comprising a fifth catalyst, wherein the fifth catalyst is one or more of an ammonia oxidation catalyst, a diesel oxidation catalyst, a catalyzed soot filter, and a selective catalytic reduction catalyst, preferably a catalyzed soot filter, the system according to any one of Embodiments 72 to 75.

[0214] 77. The fifth catalyst has an inlet end and an outlet end, and is provided with a coating on a fifth substrate, preferably a wall-flow filter substrate. In the exhaust gas treatment system, the fifth catalyst is disposed downstream of the fourth catalyst, and the inlet end of the fifth catalyst is disposed upstream of the outlet end of the fifth catalyst. The outlet end of the fourth catalyst is in fluid communication with the inlet end of the fifth catalyst. In the exhaust gas treatment system, no catalyst for treating the exhaust gas exiting the fourth catalyst is disposed between the outlet end of the fourth catalyst and the inlet end of the fifth catalyst. The system according to Embodiment 76.

[0215] 78. Further comprising a sixth catalyst, wherein the sixth catalyst is one or more of an ammonia oxidation catalyst, a catalyzed soot filter, and a selective catalytic reduction catalyst, preferably a selective catalytic reduction catalyst. The selective catalytic reduction catalyst preferably includes one or more vanadium oxides and a zeolite material containing one or more of Cu and Fe, more preferably a zeolite material containing one or more of Cu and Fe. The system according to Embodiment 76 or 77.

[0216] 79. The sixth catalyst has an inlet end and an outlet end, and is provided with a coating on a sixth substrate. In the exhaust gas treatment system, the sixth catalyst is disposed downstream of the fifth catalyst, and the inlet end of the sixth catalyst is disposed upstream of the outlet end of the sixth catalyst. The outlet end of the fifth catalyst is in fluid communication with the inlet end of the sixth catalyst. In the exhaust gas treatment system, no catalyst for treating the exhaust gas exiting the fifth catalyst is disposed between the outlet end of the fifth catalyst and the inlet end of the sixth catalyst. The system according to Embodiment 78.

[0217] 80. Furthermore, the engine is equipped with an injection device for injecting fluid into the exhaust gas flow exiting the internal combustion engine, the injection device being located upstream of the sixth catalyst and downstream of the fifth catalyst. The system according to claim 78 or 79, wherein the fluid is preferably an aqueous urea solution.

[0218] 81. Furthermore, the system is equipped with an injection device for injecting fluid into the exhaust gas flow exiting the internal combustion engine, the injection device being located upstream of the first catalyst and downstream of the upstream end of the exhaust gas treatment system. The fluid is preferably an aqueous urea solution. The system according to any one of embodiments 1 to 80, wherein no hydrocarbon injection device is located upstream of the first catalyst and downstream of the upstream end of the exhaust gas treatment system.

[0219] A system according to any one of Embodiments 1 to 81, comprising the first catalyst described in 82.(i), the hydrocarbon injection device described in (ii), the second catalyst described in (iii), preferably the third catalyst described in (iv) as defined in any one of Embodiments 34 to 67, more preferably one or more of the fourth to sixth catalysts as defined in any one of Embodiments 72 to 79, and even more preferably the injection device(s) as defined in Embodiment 80 or 81.

[0220] 83. A method for producing a first catalyst for an exhaust gas treatment system according to any one of Embodiments 1 to 82, (a) Prepare a mixture comprising water, a solution of vanadium oxide, and a first oxide material containing titanium. (b) The mixture obtained in (a) is placed on the surface of the inner wall of a first substrate to obtain a slurry-treated substrate, wherein the first substrate has an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the first substrate, and comprises a plurality of passages defined by the inner wall, wherein the interface between the passage and the inner wall is defined by the surface of the inner wall. (c) Optionally, dry the slurry-treated substrate obtained in (b) to obtain a substrate on which the coating is placed. (d) The slurry-treated substrate obtained in (b), preferably the dried slurry-treated substrate obtained in (c), is fired to obtain a coated substrate. Includes, Also, optionally, (b') The mixture obtained in (a) is placed on the surface of the coating placed on the substrate obtained in (d). (c')Optionally, dry the slurry-treated substrate obtained in (b'). The slurry-treated substrate obtained in (d')(b'), or the dried slurry-treated substrate obtained in (c'), is fired. Includes, From (d) or (d'), obtain the first catalyst. method.

[0221] 84. The above (a) is, (a.1) Prepare a mixture comprising water and a first oxide support containing titanium, wherein the first oxide support further comprises one or more of tungsten, silicon, zirconium, and antimony, more preferably one or more of tungsten, silicon, and antimony. (a.2) Add a solution of vanadium oxide, preferably one or more solutions of vanadium oxalate, ammonium vanadate, and vanadium oxide, more preferably a solution of vanadium oxalate, to the mixture obtained in (a.1). (a.3) Preferably, an oxide binder source is added, where the oxide binder source is one or more of colloidal silica, alumina, and zirconia, and more preferably colloidal silica. The method of embodiment 83, including the method of embodiment 83.

[0222] 85. The method of Embodiment 83 or 84, wherein (b) above comprises arranging the mixture over 95-100%, more preferably 98-100%, and even more preferably 99-100% of the axial length of the substrate.

[0223] The method according to any one of Embodiments 83 to 85, wherein the arrangement of the mixture described in (b) is carried out by spraying the mixture onto the substrate or immersing the substrate in the mixture, preferably by immersing the substrate in the mixture.

[0224] The method according to any one of Embodiments 83 to 86, wherein the drying described in (c) is carried out in a gas atmosphere having a temperature in the range of 90 to 200 °C, preferably in the range of 120 to 160 °C.

[0225] The method according to any one of Embodiments 83 to 87, wherein the drying described in (c) is carried out for a duration in the range of 5 minutes to 300 minutes, preferably in the range of 20 minutes to 60 minutes, in a gas atmosphere.

[0226] The method according to any one of Embodiments 83 to 88, wherein the dried slurry-treated substrate obtained in (c) has a moisture content in the range of 0 to 30%, preferably in the range of 5 to 25%, more preferably in the range of 15 to 20%.

[0227] The method according to any one of Embodiments 87 to 89, wherein the gas atmosphere is one or more of air, lean air, and oxygen, more preferably contains air, preferably.

[0228] The method according to any one of Embodiments 83 to 90, wherein the firing described in (d) is carried out in a gas atmosphere having a temperature in the range of 300 to 600 °C, preferably in the range of 400 to 550 °C.

[0229] The method according to any one of Embodiments 83 to 91, wherein the firing described in (d) is carried out for a duration in the range of 5 minutes to 120 minutes, preferably in the range of 20 minutes to 40 minutes, in a gas atmosphere.

[0230] The method according to Embodiment 91 or 92, wherein the gas atmosphere is one or more of air, lean air, and oxygen, more preferably contains air (preferably).

[0231] 94. The method according to any one of embodiments 83 to 93, wherein (b') comprises arranging the mixture over 95 to 100%, more preferably 98 to 100%, and even more preferably 99 to 100% of the axial length of the substrate.

[0232] The method according to any one of embodiments 83 to 94, wherein the arrangement of the mixture described in 95.(b') is carried out by spraying the mixture onto a substrate or by immersing the substrate in the mixture, preferably by immersing the substrate in the mixture.

[0233] The method according to any one of embodiments 83 to 95, wherein the drying described in 96.(c') is carried out in a gas atmosphere having a temperature in the range of 90 to 200°C, preferably in the range of 120 to 160°C.

[0234] The method according to any one of embodiments 83 to 96, wherein the drying described in 97.(c') is carried out in a gas atmosphere for a duration ranging from 5 minutes to 300 minutes, preferably ranging from 20 minutes to 60 minutes.

[0235] The method according to any one of Embodiments 83 to 97, wherein the dried slurry-treated substrate obtained in 98.(c') has a moisture content in the range of 0 to 30%, preferably in the range of 5 to 25%, and more preferably in the range of 15 to 20%.

[0236] 99. The method according to Embodiment 96 or 97, wherein the gas atmosphere is one or more of air, dilute air, and oxygen, more preferably containing air.

[0237] The method according to any one of embodiments 83 to 99, wherein the firing described in 100.(d') is carried out in a gas atmosphere having a temperature in the range of 300 to 600°C, preferably in the range of 400 to 550°C.

[0238] The method according to any one of Embodiments 83 to 100, wherein the firing described in 101.(d') is carried out in a gas atmosphere for a duration of 5 to 120 minutes, preferably 20 to 40 minutes.

[0239] 102. The method according to Embodiment 100 or 101, wherein the gas atmosphere is one or more of air, dilute air, and oxygen, more preferably containing air.

[0240] 103. The method according to any one of embodiments 83 to 102, comprising (a), (b), (c), (d) and optionally (b'), (c'), and (d').

[0241] 104. A catalyst in an exhaust gas treatment system according to any one of Embodiments 1 to 82, preferably the first catalyst according to (i), which is obtained or can be obtained by the method described in any one of Embodiments 83 to 103.

[0242] 105. Use of the catalyst described in Embodiment 104 for the selective catalytic reduction of NOx.

[0243] 106. Use of the exhaust gas treatment according to any one of Embodiments 1 to 82 for treating exhaust gas flow discharged from an internal combustion engine, preferably a diesel engine.

[0244] 107. A method for treating exhaust gas flow discharged from an internal combustion engine, (1) Prepare an exhaust gas flow from an internal combustion engine, preferably a diesel engine, wherein the exhaust gas flow contains one or more of NOx, ammonia, nitric oxide, and hydrocarbons. (2) Pass the exhaust gas flow prepared in (1) through the exhaust gas system described in any one of Embodiments 1 to 82. A method that includes this.

[0245] In relation to the present invention, the term “interior wall surface” should be understood as the “bare,” “exposed,” or “empty” surface of the wall, i.e., the untreated surface of the wall made of the wall material, excluding any unavoidable impurities that may contaminate the surface.

[0246] Furthermore, in relation to the present invention, the phrase "X is one or more of A, B, and C" is understood to disclose that X is either A or B or C, A and B, A and C, B and C, or A and B and C, where X is a given feature and A, B, and C each represent a specific realization of the feature. In this regard, a person skilled in the art should note that they can translate the above abstract terms into concrete examples. For example, X could be a chemical element and A, B, and C could be specific elements such as Li, Na, and K, or X could be a temperature and A, B, and C could be specific temperatures such as 10°C, 20°C, and 30°C, and so on. In this regard, a person skilled in the art should also note that they can further extend the above terms to less specific realizations of the features. For example, "X is one or more of A and B" discloses that X is either A or B, or A and B. It should be noted that the above terms can also be extended to more specific realizations of the features in question. For example, "X is one or more of A, B, C, and D" discloses that X is either A or B or C or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D.

[0247] In relation to the present invention, the phrase "no catalyst is located downstream of the outlet end of catalyst X" should be understood as meaning that neither catalyst nor catalytic components are located downstream of the outlet end of catalyst X. However, this does not preclude the existence of one or more injection devices as illustrated by embodiments of the present invention.

[0248] In relation to the present invention, the term "width of the base material" should be understood to mean the diameter of the base material when the base material is cylindrical.

[0249] In relation to the present invention, the term "consists of" in relation to the mass percentage of one or more components indicates the mass percentage of the component relative to 100 mass percent of the entity in question. For example, the expression "0 to 0.001 mass percent of the coating of the first catalyst consists of palladium" indicates that 0 to 0.001 mass percent of the components constituting the coating are palladium.

[0250] In connection with the present invention, the term "close-coupled" catalyst is used to define a catalyst that is the first catalyst to receive the exhaust gas flow from the engine (the catalyst is installed close to—immediately adjacent to—the engine, without any other catalytic components in between).

[0251] In relation to the present invention, the term "internal combustion engine" refers to a diesel engine or a gasoline engine, and preferably a diesel engine.

[0252] The present invention will be further explained by the following reference examples, comparative examples, and examples. [Examples]

[0253] Reference Example 1: Measurement of Particle Size Distribution (Dv90) The particle size distribution was measured using static light scattering with a Sympatec HELOS instrument. The optical density of the sample ranged from 5% to 10%.

[0254] Reference Example 2: Preparation of CuCHA Zeolite The Cu-containing skeletal structure-type CHA zeolite material used in the examples herein was prepared according to the teachings of US8293199B2. For details, see Example 2 of US8293199B2, column 15, lines 26-52.

[0255] Reference Example 3: Measurement of BET specific surface area The BET specific surface area of ​​alumina was measured using liquid nitrogen according to DIN66131 or DINISO9277.

[0256] Reference Example 4: Preparation of a vanadium-containing SCR catalyst (hereinafter referred to as "V-SCR catalyst") Doped titania powder (87% by mass TiO2, 8% by mass WO3, 5% by mass SiO2, BET specific surface area 85 m²) 2 Vanadium oxalate and colloidal silica were added to an aqueous mixture of 2.5 micrometers / g (Dv90), and based on the mass of titania + tungsten oxide + silica in the catalyst after calcination, 5% by mass of V2O5 and 2% by mass of silica (from colloidal silica) in the catalyst after calcination were obtained. A portion of the final slurry was placed over the entire length of an uncoated honeycomb flow-through cordierite monolith substrate according to a method well known in the art (a cylindrical substrate with a diameter of 26.67 cm (10.5 inches) × length of 15.24 cm (6 inches), with a density of 400 / (2.54) per square centimeter). 2 (Each cell has a wall thickness of 0.14 mm (5.5 mil)). After drying and calcining the coated substrate, the remaining portion of the final slurry is placed over the entire length of the coated substrate, followed by drying and calcining, to obtain approximately 4.5 g / in of catalyst. 3 The final amount of coating was obtained.

[0257] The catalytic activity (NOx conversion rate) of the obtained catalyst was measured and is shown in Figure 1.

[0258] Reference Example 5: Preparation of a palladium-containing diesel oxidation catalyst (hereinafter referred to as "Pd-DOC") Zr-doped alumina powder (20% by mass of ZrO2, BET200m 2Palladium nitrate solution was added to a mixture of Pd / g, Dv90 of 125 microns, and total pore volume of 0.425 ml / g. After calcination at 590°C, the Pd content of the final Pd / Zr-alumina was 1.5% by mass, based on the mass of Zr-alumina. This material was added to water, and the resulting slurry was ground until the resulting Dv90 was 10 microns, as described in Reference Example 1. The final slurry was placed over the entire length of an uncoated honeycomb flow-through cordierite monolith substrate according to a method well known in the art (a cylindrical substrate with a diameter of 26.67 cm (10.5 inches) × length of 7.62 cm (3 inches), with a cell count of 400 / (2.54)). 2 (The sample was made from a sample of 0.1 mm (4 mil) of wall thickness per square centimeter. The substrate was then dried and calcined. The amount of post-calcination coating in the catalyst was approximately 91 g / l (1.5 g / in). 3 ) and Pd are 40g / ft 3 That was the case.

[0259] Reference Example 6: Preparation of a copper-containing SCR catalyst (hereinafter referred to as "Cu-SCR").

[0260] A zirconyl acetate solution was added to an aqueous slurry of Cu-CHA (calculated as CuO, with 5.1 mass% Cu and a molar ratio of SiO2:Al2O3 of 18), and 5 mass% ZrO2 was achieved in the catalyst after calcination, based on the mass of Cu-CHA. This final slurry was placed over the entire length of an uncoated honeycomb flow-through cordierite monolith substrate according to a method well known in the art (a cylindrical substrate with a diameter of 26.67 cm (10.5 inches) × length of 15.24 cm (6 inches), with a cell count of 400 / (2.54) per square centimeter). 2 (with a wall thickness of 0.1 mm (4 mil)). The substrate was then dried and fired. The load volume after firing was 128.15 g / l (2.1 g / in). 3 ) was.

[0261] Reference Example 8.1: Comparative test of the V-SCR catalyst from Reference Example 4 and the Cu-SCR catalyst from Reference Example 6 The DeNOx output of catalysts from Reference Examples 4 and 6 was measured at 210°C and a space velocity of 50,000 / h to investigate the responsiveness of the catalyst from Reference Example 4 (V-SCR catalyst) and the catalyst from Reference Example 6 (Cu-SCR catalyst). Both the V-SCR catalyst and the Cu-SCR catalyst were tested under steady-state conditions in an engine in a test cell with an engine output level of approximately 550 ppm NOx. As can be seen from Figure 2, the V-SCR catalyst showed the maximum NOx conversion rate after approximately 600 seconds. From this figure, it can be seen that the V-SCR catalyst from Reference Example 4 is more responsive than the Cu-SCR catalyst from Reference Example 6. Without being constrained by any particular theory, it can be assumed that the V-SCR catalyst has a faster response at low ammonia storage levels and lower ammonia storage levels compared to the Cu-SCR catalyst.

[0262] Therefore, Reference Example 8.1 demonstrated that, when high-speed response is required, the V-SCR catalyst (Reference Example 4) is a superior candidate for a close-coupled catalyst compared to the Cu-SCR catalyst (Reference Example 6).

[0263] Comparative Example 1: Fabrication of an exhaust gas treatment system other than the present invention By combining the catalyst of Reference Example 4 ("V-SCR catalyst") and the catalyst of Reference Example 5 ("Pd-DOC"), positioning the catalyst of Reference Example 5 downstream of Reference Example 4, and installing a hydrocarbon (HC) injection device upstream of the catalyst of Reference Example 4, an exhaust gas treatment device other than the present invention was fabricated.

[0264] Example 1: Fabrication of an exhaust gas treatment system according to the present invention The catalyst of Reference Example 4 ("V-SCR catalyst") and the catalyst of Reference Example 5 ("Pd-DOC") were combined, the catalyst of Reference Example 5 was positioned downstream of the catalyst of Reference Example 4, and a hydrocarbon (HC) injection device was installed downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 5 to produce the exhaust gas treatment device according to the present invention.

[0265] Example 2: Use of the exhaust gas treatment system of Example 1 and Comparative Example 1 - Control of heat generation (exotherms) within the system The temperatures at the inlet and outlet ends of the V-SCR catalysts in these two systems, as well as the temperatures at the inlet and outlet ends of the Pd-DOC in both systems, were measured. The exhaust gas treatment systems were installed in a close-coupled position directly downstream of the engine. HC was injected via an HC injector. The injection times are shown in Figures 4 and 5.

[0266] Figure 4 shows the inlet and outlet temperatures of the V-SCR catalyst and the outlet temperature of Pd-DOC as a function of time in the exhaust gas treatment system of Comparative Example 1, when the HC injection device is placed in front of the V-SCR catalyst. At low temperatures, i.e., below 300°C, the V-SCR generates only a small amount of heat, and most of the heat generation appears to be concentrated in the Pd-DOC. After approximately 58 minutes, HC injection is stopped, and the temperature of the inlet end of the V-SCR is increased. Without being bound by any particular theory, it is thought that at low temperatures, some of the HC is adsorbed onto the V-SCR, and as the temperature rises, the adsorbed HC is oxidized on the V-SCR catalyst, generating uncontrollable heat generation at temperatures exceeding 600°C. Thus, the V-SCR is exposed to temperatures outside its operation window. As a result, the support of the catalyst may sinter, reducing its surface area, and thus potentially causing it to lose its activity. Furthermore, as mentioned above, exposure to 600°C may also cause vanadium sublimation.

[0267] Figure 5 shows the inlet temperatures of the V-SCR and Pd-DOC, and the outlet temperature of Pd-DOC, as a function of time, for the system according to the present invention, when the HC injector is positioned downstream of the V-SCR catalyst and upstream of the Pd-DOC. Even when the inlet temperature was increased by stopping the injection of HC, no excessive heat generation was observed. This suggests that HC is adsorbed on the Pd-DOC without oxidation. By positioning the HC injector after the V-SCR, high concentrations of HC do not pass through the V-SCR, thus ensuring that the V-SCR does not adsorb HC during the active regeneration event. Therefore, Example 2 shows that, in addition to providing an exhaust gas treatment system with a (cc)V-SCR at a proximal connection position, it is important to install the HC injector downstream of the cc-V-SCR, thereby maintaining the efficiency and durability of the exhaust gas treatment system.

[0268] Reference Example 7: Preparation of AMOX catalyst Zr-doped alumina powder (20% by mass of ZrO2, BET200m 2 Platinum ammine solution was added to a mixture of Pt / Zr-alumina (Dv90 125 microns, total pore volume 0.425 ml / g). After calcination at 590°C, the final Pt content of the Pt / Zr-alumina was 1.85% by mass, based on the mass of Zr-alumina. This material was added to water, and the resulting slurry was ground until the resulting Dv90 was 10 microns, as described in Reference Example 1. Zirconyl acetate solution was added to an aqueous slurry of Cu-CHA (calculated as CuO, with Cu content of 5.1% by mass and a molar ratio of SiO2:Al2O3 of 18) to achieve 5% by mass of ZrO2 based on the mass of Cu-CHA after calcination. The ground Pt / Zr-alumina slurry was added to the Zr / Cu-CHA slurry and mixed. This final slurry is then applied to an uncoated flow-through honeycomb cordierite monolith substrate (diameter: 26.67 cm (10.5 inches) x length: 7.62 cm (3 inches), 400 / (2.54) per square centimeter. 2The catalyst was arranged along the entire length of a cylindrical substrate with a wall thickness of 0.1 mm (4 mils). The substrate was then dried and calcined. The amount of coating in the catalyst after calcination was approximately 3.0 g / in. 3 It was 15.26 g / l (0.25 g / in). 3 ) 0.28 g / l (8 g / ft) on Zr-alumina 3 The amount of Pt loaded, and 158.66 g / l (2.6 g / in) 3 ) Cu-CHA+ 7.93g / l (0.13g / in) 3 It contains ZrO2.

[0269] Reference Example 8.2: Testing of an exhaust gas treatment system using a cc-V-SCR catalyst or a cc-Cu-SCR catalyst - Sulfation resistance A first exhaust gas treatment system (System 1) was fabricated by combining the catalyst from Reference Example 4 (V-SCR catalyst) and the catalyst from Reference Example 7, with the catalyst from Reference Example 7 positioned downstream of the V-SCR catalyst. A second exhaust gas treatment system (System 2) was fabricated by combining the catalyst from Reference Example 6 (Cu-SCR catalyst) and the catalyst from Reference Example 7, with the catalyst from Reference Example 7 positioned downstream of the Cu-SCR catalyst. NOx conversion rates were measured over 200 hours of simulated low-load driving at 215°C under steady-state conditions (engine output NOx = 250 ppm, SV = 40 k / h, ammonia to NOx ratio (ANR) 0.85). The results are shown in Figure 6.

[0270] As shown in Figure 6, the second system using the cc-Cu-SCR catalyst showed an initial NOx conversion rate of approximately 60%, which decreased to about 40% after 200 hours of low-temperature operation. The first system equipped with the cc-V-SCR catalyst showed an initial NOx conversion rate of approximately 73%, which remained stable at 66-68% for over 200 hours. Therefore, this example demonstrates that a hybrid system with cc-V-SCR containing Cu-CHA-containing AMOX is more stable than a system with cc-Cu-CHA containing Cu-CHA-containing AMOX as the downstream catalyst. While we do not wish to be bound by specific theories, it is believed that the cc-V-SCR catalyst reduces the effects of sulfation and hydrocarbon fouling in exhaust gas treatment systems.

[0271] Example 3: Fabrication of the exhaust gas treatment system according to the present invention An exhaust gas treatment system according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst"), a hydrocarbon (HC) injection device, the catalyst of Reference Example 5 ("Pd-DOC"), and the catalyst of Reference Example 6 ("Cu-SCR catalyst") in series. In this case, the catalyst of Reference Example 5 was positioned downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 6 was positioned downstream of the catalyst of Reference Example 5, and the HC injection device was installed downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 5.

[0272] Reference Example 9: Preparation of a palladium-containing SCR catalyst ("Pd / ZrO2-Cu-SCR catalyst") Palladium nitrate solution is added to zirconium oxide (pore volume 0.420 ml / g). After calcination at 590 °C, the final Pd / zirconia had a Pd content of 3.5 wt% based on the mass of Zr-alumina. This material was added to water, and the resulting slurry was pulverized until the obtained Dv90 became 10 microns as described in Reference Example 1. To an aqueous slurry of Cu-CHA prepared according to Reference Example 2 (about 3 wt% Cu calculated as CuO, molar ratio of SiO2:Al2O3 about 32), a zirconyl-acetate solution was added so that the calcined ZrO2 became 5 wt%. This mixture was spray-dried and pulverized until the obtained Dv90 became 5 microns as described in Reference Example 1. The pulverized Pd / ZrO2 slurry was added to the Zr / Cu-CHA slurry and mixed. The final slurry was placed over the entire length of an uncoated honeycomb flow-through cordierite monolith substrate (diameter: 26.67 cm (10.5 inches) × length: 7.62 cm (3 inches), number of cells per square centimeter 400 / (2.54) 2 of the cell number, cylindrical substrate with a wall thickness of 0.1 millimeter (4 mils)). Then, the substrate was dried and calcined. The loading amount of the calcined coating in the catalyst was about 3.0 g / in 3 . 1.06 g / l (30 g / ft 3 ) of Pd was supported on 30.51 g / l (0.5 g / in 3 ) of ZrO2, and it consisted of 144.02 g / l (2.36 g / in 3 ) of Cu-CHA plus 7.32 g / l (0.12 g / in 3 ) of ZrO2.

[0273] Reference Example 10: Preparation of an AMOX catalyst with a mass ratio of Pt:Pd of 10:1 Zr-doped alumina powder (ZrO2 is 20 wt%, BET 200 m 2To (g, Dv90 being 125 μm, total pore volume 0.425 ml / g), a platinum ammine solution and a palladium nitrate solution were added at a Pt:Pd mass ratio of 10:1. After calcination at 590 °C, the final Pd / Zr-alumina contained 1.85 mass% of Pd and Pt based on the mass of Zr-alumina, and the Pt:Pd mass ratio was 10:1. This material was added to water, and the resulting slurry was pulverized until the obtained Dv90 became 10 μm as described in Reference Example 1. To an aqueous slurry of Cu-CHA prepared according to Reference Example 2 (Cu being about 3 mass% calculated as CuO, molar ratio of SiO2:Al2O3 being about 32), a zirconyl-acetate solution was added so that ZrO2 became 5 mass% based on the mass of Cu-CHA after calcination. This mixture was spray-dried and pulverized until the obtained Dv90 became 5 μm as described in Reference Example 1. The pulverized Pd / Zr-alumina slurry was added to the Zr / Cu-CHA slurry and mixed. This final slurry was then placed over the entire length of an uncoated through-flow honeycomb cordierite monolith substrate (diameter: 26.67 cm (10.5 inches) × length: 7.62 cm (3 inches), number of cells per square centimeter 400 / (2.54) 2 of the cell number, cylindrical substrate with a wall thickness of 0.1 millimeter (4 mils)). Then, the substrate was dried and calcined. The loading amount of the coating after calcination in this catalyst was about 3 g / in 3 where Cu-CHA was 2.75 g / in 3 ZrO2 was 0.13 g / in 3 Zr-alumina was 0.25 g / in 3 Pt + Pd was 8 g / ft 3 was contained.

[0274] Example 4: Fabrication of an exhaust gas treatment system according to the present invention An exhaust gas treatment system according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst"), a hydrocarbon (HC) injection device, the catalyst of Reference Example 9 ("Pd / ZrO2-Cu-SCR catalyst"), and the catalyst of Reference Example 10 ("AMOX catalyst") in series. Here, the catalyst of Reference Example 9 was located downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 10 was located downstream of the catalyst of Reference Example 9, and the HC injection device was located downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 9.

[0275] Example 5: Fabrication of an exhaust gas treatment system according to the present invention An exhaust gas treatment system according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst"), a hydrocarbon (HC) injection device, the catalyst of Reference Example 5 ("Pd-DOC"), the catalyst of Reference Example 6 ("Cu-SCR catalyst"), and the catalyst of Reference Example 7 ("AMOX catalyst") in series. Here, the catalyst of Reference Example 5 was located downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 6 was located downstream of the catalyst of Reference Example 5, the catalyst of Reference Example 7 was located downstream of the catalyst of Reference Example 6, and the HC injection device was located downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 5.

[0276] Example 6: Fabrication of the exhaust gas treatment system according to the present invention An exhaust gas treatment system according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst"), a hydrocarbon (HC) injection device, the catalyst of Reference Example 5 ("Pd-DOC"), the catalyst of Reference Example 9 ("Pd / ZrO2-Cu-SCR catalyst"), and the catalyst of Reference Example 10 ("AMOX catalyst") in series. Here, the catalyst of Reference Example 5 was located downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 9 was located downstream of the catalyst of Reference Example 5, the catalyst of Reference Example 10 was located downstream of the catalyst of Reference Example 9, and the HC injection device was located downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 5.

[0277] Reference Example 11: Preparation of a palladium-containing diesel oxidation catalyst (hereinafter referred to as "Pd-DOC2") Except for reducing the amount of palladium used, the Pd-DOC of Reference Example 11 was prepared in the same manner as the Pd-DOC of Reference Example 5. The amount of post-calcination coating in the catalyst was approximately 91 g / l (1.5 g / in). 3 ) with Pd at 30g / ft 3 That was the case.

[0278] Example 7: Fabrication of an exhaust gas treatment system according to the present invention An exhaust gas treatment system according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst" - Cat.1), a hydrocarbon (HC) injection device, the catalyst of Reference Example 11 ("Pd-DOC2" - Cat.2), and the catalyst of Reference Example 6 ("Cu-SCR catalyst" - Cat.3) in series. In this case, the catalyst of Reference Example 11 was located downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 6 was located downstream of the catalyst of Reference Example 11, and the HC injection device was located downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 11.

[0279] Example 8: Fabrication of an exhaust gas treatment system according to the present invention An exhaust gas treatment system according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst" - Cat.1), a hydrocarbon (HC) injection device, the catalyst of Reference Example 9 ("Pd / ZrO2-Cu-SCR catalyst" - Cat.2), and the catalyst of Reference Example 6 ("Cu-SCR catalyst" - Cat.3) in series. In this case, the catalyst of Reference Example 9 was located downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 6 was located downstream of the catalyst of Reference Example 9, and the HC injection device was located downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 9.

[0280] Reference Example 12: Preparation of a platinum-containing diesel oxidation catalyst (hereinafter referred to as "Pt-DOC") Titania powder (TiO2 100% by mass, BET specific surface area 200m 2 Platinum ammine solution was wet-impregnated into a material ( / g, Dv90 20 micrometers). The amount of titania was 0.75 g / in of titania in the catalyst after calcination. 3The calculations were made to achieve this. After firing at 590°C, the final Pt content of the Pt / TiO2 was approximately 1.7 mass%, based on the mass of titania. This material was added to acetic acid and water to form a Pt / titania slurry. In parallel with this, alumina (100 mass%, BET specific surface area approximately 200 m²) was added. 2 A binder slurry was prepared by mixing alumina ( / g) with a diluted solution of nitric acid (HNO3). The amount of alumina was determined by the amount of alumina loaded into the catalyst after calcination, which was 0.2 g / in. 3 The calculation was performed to achieve the following. Zirconium acetate solution (a mixture of acetic acid and zirconium hydroxide) was added to this alumina slurry. The amount of alumina was calculated to be 0.25 g / in of the alumina loaded into the catalyst after calcination. 3 The calculations were performed to achieve the following result. The resulting mixture was ground until the Dv90, measured using the method described in Reference Example 1, was 10 microns. Finally, the Al / Zr mixture and the Pt / TiO2 slurry were mixed with octanol to form a final slurry with a pH of approximately 4.5.

[0281] This final slurry was then placed over the entire length of an uncoated honeycomb flow-through cordierite monolith substrate according to a method well known in the art (a cylindrical substrate with a diameter of 26.67 cm (10.5 inches) × length of 7.62 cm (3 inches), with 400 cells per square centimeter / (2.54)). 2 (with a wall thickness of 0.1 mm (4 mil)). The substrate was then dried and calcined. The amount of coating loaded into the catalyst after calcination was approximately 62 g / l (approximately 1 g / in). 3 ), Pt is approximately 22g / ft 3 That was the case.

[0282] Comparative Example 2: Fabrication of an exhaust gas treatment system other than the present invention An exhaust gas treatment system not according to the present invention was fabricated by combining the catalyst of Reference Example 4 ("V-SCR catalyst" - Cat.1), a hydrocarbon (HC) injection device, the catalyst of Reference Example 12 ("Pt-DOC" - Cat.2), and the catalyst of Reference Example 6 ("Cu-SCR catalyst" - Cat.3) in series. In this system, the catalyst of Reference Example 12 was located downstream of the catalyst of Reference Example 4, the catalyst of Reference Example 6 was located downstream of the catalyst of Reference Example 12, and the HC injection device was located downstream of the catalyst of Reference Example 4 and upstream of the catalyst of Reference Example 12.

[0283] Example 9: Use of the exhaust gas treatment systems of Examples 7, 8 and Comparative Example 2 - Generation of DeNOx and N2O The exhaust gas treatment systems of Example 7 (System A), Example 8 (System B), and Comparative Example 2 (System C) were tested under steady-state conditions (load point: 290°C, space velocity: 1100 kg / h, E.O.NOx = 670 ppm) and transient conditions (WHTC test cycle with EO (engine out) NOx around 300 g (cum), average temperature during the cycle at 235°C - Tmax = 330°C; Tmin = 170°C - ANR (ammonia / NOx ratio) = 1.05). The results are shown in Figures 7 to 10.

[0284] Figures 7 and 8 show that even when Pt / TiO2 (Pt-DOC) is used as the second catalyst (Cat.2) in the exhaust gas treatment system, the NOx conversion rate measured at the outlet end of Cat.2 does not decrease significantly. Furthermore, it shows that exhaust gas treatment system C (not the one according to the present invention) yields a NOx conversion rate at least 10% lower at its outlet end. Moreover, it shows that using Pt / TiO2 (Pt-DOC) as the second catalyst (Cat.2) dramatically increases the amount of nitrous oxide produced at the outlet ends of both the second catalyst (Cat.2) and the third catalyst (Cat.3). The comparative results can be seen in Figures 9 and 10. While we do not wish to be bound by any particular theory, it is thought that the second catalyst, consisting of Pt / TiO2, oxidizes the reductant (ammonia) that has slipped through the first catalyst into nitrous oxide, resulting in a decrease in the NOx conversion rate at the system's outlet end. Therefore, Example 9 demonstrates that using Pd-DOC or Pd / ZrO2-Cu-SCR as a second catalyst in an exhaust gas treatment system can significantly reduce nitrous oxide production while improving the NOx reduction rate, compared to a second catalyst with platinum supported on titania. Cited literature -US2017 / 152780A1 -US2018 / 258811A1 -WO2018 / 224651A2

Claims

1. An exhaust gas treatment system for treating the exhaust gas flow discharged from an internal combustion engine, wherein the exhaust gas treatment system has an upstream end for introducing the exhaust gas flow into the exhaust gas treatment system, and the exhaust gas treatment system (i) A first catalyst having an inlet end and an outlet end, and comprising a coating and a first substrate, wherein the first substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axis direction extending from the inlet end to the outlet end of the first substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the first substrate, and the coating comprises vanadium oxide supported on a first oxide carrier containing titanium, (ii) A hydrocarbon injection device for injecting a hydrocarbon-containing fluid into the exhaust gas flow exiting the outlet end of the first catalyst described in (i), (iii) A second catalyst having an inlet end and an outlet end, and comprising a coating and a second substrate, wherein the second substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the second substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the second substrate, and the coating comprises palladium supported on a second oxide carrier containing one or more of zirconium, silicon, and aluminum, (iv) A third catalyst having an inlet end and an outlet end, and comprising a coating and a third substrate, wherein the third substrate comprises a plurality of passages having an inlet end, an outlet end, and a length in the substrate axial direction extending from the inlet end to the outlet end of the third substrate, and the interface between the passages and the inner wall is defined by the surface of the inner wall, wherein the coating is disposed on the surface of the inner wall of the third substrate, and the coating comprises a zeolite material having a skeletal CHA and containing Cu, It is equipped with, Here, the first catalyst described in (i) is a first catalyst of an exhaust gas treatment system installed downstream of the upstream end of the exhaust gas treatment system, and the inlet end of the first catalyst is located upstream of the outlet end of the first catalyst. Here, in the exhaust gas treatment system, the second catalyst described in (iii) is located downstream of the first catalyst described in (i) and downstream of the hydrocarbon injection device described in (ii), and the inlet end of the second catalyst is located upstream of the outlet end of the second catalyst. Here, in the exhaust gas treatment system, the third catalyst described in (iv) is located downstream of the second catalyst described in (iii), and the inlet end of the third catalyst is located upstream of the outlet end of the third catalyst. An exhaust gas treatment system characterized by the following features.

2. The system according to claim 1, wherein the coating of the first catalyst contains the vanadium oxide in an amount ranging from 1.0 to 10% by mass, based on the mass of the first oxide support.

3. The system according to claim 1 or 2, wherein the first oxide support containing titanium further comprises one or more of tungsten, silicon, zirconium, and antimony.

4. The system according to any one of claims 1 to 3, wherein the second oxide support included in the coating of the second catalyst described in (iii) comprises one or more of zirconium and aluminum.

5. The coating of the second catalyst described in (iii) is 5 to 90 g / ft ３ The system according to any one of claims 1 to 4, comprising palladium in an amount within the range.

6. The system according to claim 5, wherein palladium is the only platinum group metal present in the coating of the second catalyst described in (iii).

7. The system according to any one of claims 1 to 6, wherein 98 to 100% by mass of the coating of the second catalyst consists of palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium.

8. The system according to any one of claims 1 to 6, wherein the coating of the second catalyst described in (iii) further comprises a zeolite material, the zeolite material containing one or more of Cu and Fe.

9. The system according to claim 8, wherein the coating of the second catalyst described in (iii) further comprises an oxide binder.

10. The exhaust gas treatment system according to any one of claims 1 to 9, wherein the outlet end of the second catalyst described in (iii) is in fluid communication with the inlet end of the third catalyst described in (iv), and no catalyst for treating the exhaust gas flow leaving the second catalyst is disposed between the outlet end of the second catalyst described in (iii) and the inlet end of the third catalyst described in (iv).

11. The system according to any one of claims 1 to 10, wherein the coating of the second catalyst described in (iii) comprises palladium supported on a second oxide support containing one or more of zirconium, silicon, aluminum, and titanium, and wherein the coating of the third catalyst described in (iv) comprises a zeolite material containing one or more of Cu and Fe.

12. The system further comprises a fourth catalyst, the fourth catalyst being one or more of an ammonia oxidation catalyst, a catalyst-equipped soot filter, and a selective catalytic reduction catalyst. Here, the fourth catalyst has an inlet end and an outlet end and comprises a coating and a fourth substrate, the fourth substrate having an inlet end, an outlet end and a length in the substrate axial direction extending from the inlet end to the outlet end of the fourth substrate, and comprising a plurality of passages defined by an inner wall, the interface between the passages and the inner wall being defined by the surface of the inner wall, the coating being disposed on the surface of the inner wall of the fourth substrate, and the coating containing an ammonia oxidizing component, Herein, in the exhaust gas treatment system, the fourth catalyst is located downstream of the third catalyst described in (iv), and the inlet end of the fourth catalyst is located upstream of the outlet end of the fourth catalyst, according to any one of claims 1 to 11.

13. Furthermore, it is equipped with an injection device that injects fluid into the exhaust gas flow exiting the internal combustion engine, and the injection device is located upstream of the first catalyst and downstream of the upstream end of the exhaust gas treatment system. Here, the fluid is an aqueous urea solution. The system according to any one of claims 1 to 11, wherein no hydrocarbon injection device is located upstream of the first catalyst and downstream of the upstream end of the exhaust gas treatment system.

14. A method for treating exhaust gas flow from an internal combustion engine, (1) Prepare an exhaust gas stream from an internal combustion engine, wherein the exhaust gas stream contains one or more of NOx, ammonia, nitric oxide, and hydrocarbons. (2) Pass the exhaust gas flow prepared in (1) through the exhaust gas treatment system described in any one of claims 1 to 13. A method characterized by including the following.

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