High ammonia storage capacity SCR catalysts
The present invention relates to a catalyst for the selective catalytic reduction of nitrogen oxide, the catalyst comprising a first coating comprising a 12-membered ring pore zeolitic material comprising a first metal which is one or more of copper and iron, and a second coating comprising an 8-membered ring pore zeolitic material comprising a second metal which is one or more of copper and iron.
1. A catalyst for selective catalytic reduction of nitrogen oxide comprising:
(i) a substrate comprising an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by internal walls of the substrate extending therethrough;
(ii) a first coating comprising a 12-membered ring pore zeolitic material comprising a first metal which is one or more of copper and iron, wherein the 12-membered ring pore zeolitic material comprises the first metal in an amount of z1 weight-%, calculated as the weight of the first metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 12-membered ring pore zeolitic material comprising the first metal;
(iii) a second coating comprising an 8-membered ring pore zeolitic material comprising a second metal which is one or more of copper and iron, wherein the 8-membered ring pore zeolitic material comprises the second metal in an amount of z2 weight-%, calculated as the weight of the second metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 8-membered ring pore zeolitic material comprising the second metal;
wherein the first coating is disposed on the surface of the internal walls of the substrate, which surface defines the interface between the internal walls and the passages, and extends over x % of the substrate axial length from the inlet end toward the outlet end of the substrate, wherein x ranges from 10 to 75;
wherein the second coating extends over y % of the substrate axial length from the outlet end toward the inlet end of the substrate, wherein y ranges from 25 to 90;
wherein the ratio z1:z2 is in the range of from 0.5:1 to 0.95:1.
2. The catalyst of claim 1 , wherein y is 100−x.
3. The catalyst of claim 1 , wherein the 12-membered ring pore zeolitic material contained in the first coating has a framework type selected from the group consisting of BEA, FAU, USY, GME, MOR, OFF, a mixture of two or more thereof, and a mixed type of two or more thereof.
4. The catalyst of claim 1 , wherein the 12-membered ring pore zeolitic material contained in the first coating comprises a first metal which is iron, wherein the 12-membered ring pore zeolitic material comprises iron in an amount of z1 weight-%, calculated as the weight of the first metal, calculated as Fe 2 O 3 , divided by the weight of the 12-membered ring pore zeolitic material comprising the first metal, and wherein z1 ranges of from 1.0 to 10.
5. The catalyst of claim 1 , wherein the first coating further comprises a 10-membered ring pore zeolitic material comprising a third metal which is one or more of copper and iron; and
wherein the 10-membered ring pore zeolitic material contained in the first coating has a framework type selected from the group consisting of MFI, MWW, AEL, HEU, FER, AFO, a mixture of two or more thereof, and a mixed type of two or more thereof.
6. The catalyst of claim 1 , wherein the first coating (ii) has an ammonia storage capacity A1 (NH3) of at least 2.1 mmol/g, the ammonia storage capacity determined by Thermal Gravimetric Analysis.
7. The catalyst of claim 1 , wherein the 8-membered ring pore zeolitic material contained in the second coating has a framework type selected from the group consisting of CHA, AEI, RTH, LEV, DDR, KFI, ERI, AFX, a mixture of two or more thereof, and a mixed type of two or more thereof.
8. The catalyst of claim 1 , wherein the second coating (iii) has an ammonia storage capacity A2 (NH3) of less than 2 mmol/g, the ammonia storage capacity determined by Thermal Gravimetric Analysis.
9. The catalyst of claim 1 , wherein the first coating (ii) has an ammonia storage capacity A1 (NH3) and the second coating (iii) has an ammonia storage capacity A2 (NH3) , wherein A1 (NH3) is superior to A2 (NH3) , and the ammonia storage capacity determined by Thermal Gravimetric Analysis.
10. A process for preparing a catalyst for selective catalytic reduction of nitrogen oxide comprising:
(1) providing a substrate comprising an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by internal walls of the substrate extending therethrough;
(2) preparing a first mixture comprising water and a 12-membered ring pore zeolitic material comprising a first metal which is one or more of copper and iron, wherein the 12-membered ring pore zeolitic material comprises the first metal in an amount of z1 weight-%, calculated as the weight of the first metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 12-membered ring pore zeolitic material comprising the first metal;
(3) disposing the first mixture obtained in (2) on the surface of the internal walls of the substrate provided in (1), over x % of the substrate axial length from the inlet end toward the outlet end of the substrate, wherein x ranges from 10 to 75;
(4) drying the mixture-treated substrate obtained in (3), obtaining the substrate having a first coating disposed thereon; optionally calcining;
(5) preparing a second mixture comprising water and a 8-membered ring pore zeolitic material comprising a second metal which is one or more of copper and iron, wherein the 8-membered ring pore zeolitic material comprises the second metal in an amount of z2 weight-%, calculated as the weight of the second metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 8-membered ring pore zeolitic material comprising the second metal;
(6) disposing the second mixture obtained in (5) on the substrate having a first coating disposed thereon obtained in (4) over y % of the substrate axial length from the outlet end toward the inlet end of the substrate, wherein y ranges from 25 to 90;
(7) drying the mixture-treated substrate obtained in (6), obtaining the substrate having the first coating and a second coating disposed thereon; and
(8) calcining the substrate having the first coating and the second coating disposed thereon obtained in (7), obtaining the catalyst;
wherein the ratio z1:z2 ranges from 0.5:1 to 0.95:1.
11. The process of claim 10 , wherein (2) further comprises:
(2.1) preparing a 12-membered ring pore zeolitic material;
(2.2) mixing a source of a first metal with the 12-membered ring pore zeolitic material obtained in (2.1);
(2.3) calcining the mixture obtained in (2.2), obtaining the 12-membered ring pore zeolitic material comprising the first metal;
(2.4) admixing water and the 12-membered ring pore zeolitic material comprising B the first metal.
12. An exhaust gas treatment system for treating an exhaust gas exiting from a combustion engine, wherein the system comprising one or more catalysts for the selective catalytic reduction of nitrogen oxide according to claim 1 , and one or more of a diesel oxidation catalyst, a catalyzed soot filter, and an ammonia oxidation catalyst.
13. A catalyst for selective catalytic reduction of nitrogen oxide comprising:
a substrate comprising an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by internal walls of the substrate extending therethrough, and
a coating disposed on the surface of the internal walls of the substrate, which surface defines the interface between the internal walls and the passages,
wherein the coating comprising a 12-membered ring pore zeolitic material comprising a first metal which is one or more of copper and iron, and the 12-membered ring pore zeolitic material comprises the first metal in an amount of z weight-%, calculated as the weight of the first metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 12-membered ring pore zeolitic material comprising the first metal,
wherein the coating further comprises a 10-membered ring pore zeolitic material comprising a second metal which is one or more of copper and iron, wherein the 10-membered ring pore zeolitic material comprises the second metal in an amount of y weight-%, calculated as the weight of the second metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 10-membered ring pore zeolitic material comprising the second metal; and
wherein y ranges from 0.5 to 9 and y<z.
14. The catalyst of claim 13 , wherein from 95 weight-% to 100 weight % of the framework structure of the 12-membered ring pore zeolitic material consist of Si, Al, O, and optionally H, wherein in the framework structure, the molar ratio of Si to Al, calculated as molar SiO 2 :Al 2 O 3 , is ranges from 4:1 to 20:1.
15. The catalyst of claim 13 , wherein the coating comprises the 10-membered ring pore zeolitic material comprising the second metal in an amount in the range of from 1 weight-% to 8 weight-%, based on the weight of the coating.
16. A catalyst for selective catalytic reduction of nitrogen oxide comprising:
a first catalyst for selective catalytic reduction of nitrogen oxide according to claim 13 ; and
a second catalyst for selective catalytic reduction of nitrogen oxide comprising:
a substrate comprising an inlet end, an outlet end, a substrate axial length extending from the inlet end to the outlet end, and a plurality of passages defined by internal walls of the flow through substrate extending therethrough;
a coating disposed on the surface of the internal walls of the substrate, wherein the coating comprises an 8-membered ring pore zeolitic material comprising a second metal which is one or more of copper and iron, wherein the 8-membered ring pore zeolitic material comprises the second metal in an amount of z2 weight %, calculated as the weight of the second metal, calculated as CuO and Fe 2 O 3 , divided by the weight of the 8-membered ring pore zeolitic material comprising the second metal, and wherein the second coating extends over y % of the substrate axial length from the outlet end toward the inlet end of the substrate, wherein y ranges from 25 to 90;
wherein the first catalyst is disposed upstream of the second catalyst, and
wherein there is less than 0.2 inch between the substrate of the first catalyst and the substrate of the second catalyst which are juxtaposed.