MULTIFUNCTIONAL FILTERS FOR DIESEL EMISSION CONTROL

• US 20180111089A1
• Filed: 03/30/2016
• Published: 04/26/2018
• Est. Priority Date: 03/30/2015
• Status: Active Grant

• Current Assignee: BASF Corporation (BASF SE)
• Original Assignee: BASF Corporation (BASF SE)
• Inventors: Li, Yuejin, Roth, Stanley A.
• Granted Patent: US 11,117,098 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 2255/1021 Platinum
• CPC Class Codes: B01D 2255/20761 Copper
• CPC Class Codes: B01D 2255/2092 Aluminium
• CPC Class Codes: B01D 2255/30 Silica
• CPC Class Codes: B01D 2255/50 Zeolites
• CPC Class Codes: B01D 2255/902 Multilayered catalyst
• CPC Class Codes: B01D 2255/9022 Two layers
• CPC Class Codes: B01D 2255/9025 Three layers
• CPC Class Codes: B01D 2255/903 Multi-zoned catalysts
• CPC Class Codes: B01D 2255/9032 Two zones
• CPC Class Codes: B01D 2255/9035 Three zones
• CPC Class Codes: B01D 2255/9037 More than three zones
• CPC Class Codes: B01D 2255/9155 Wall flow filters
• CPC Class Codes: B01D 2258/012 Diesel engines and lean burn gasoline engines
• CPC Class Codes: B01D 46/2429 of the honeycomb walls or cells
• CPC Class Codes: B01D 46/24491 Porosity
• CPC Class Codes: B01D 46/24492 Pore diameter
• CPC Class Codes: B01D 46/2474 of the walls along the length of the honeycomb
• CPC Class Codes: B01D 46/2482 Thickness, height, width, length or diameter
• CPC Class Codes: B01D 53/9418 for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
• CPC Class Codes: B01D 53/9436 : Ammonia
• CPC Class Codes: B01D 53/944 : Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts three-way-catalysts [TWC] B01D53/9445
• CPC Class Codes: B01D 53/945 : characterised by a specific catalyst
• CPC Class Codes: B01D 53/9468 : in different layers
• CPC Class Codes: B01D 53/9472 : in different zones
• CPC Class Codes: B01D 53/9477 : with catalysts positioned on separate bricks, e.g. exhaust systems
• CPC Class Codes: B01J 23/42 : Platinum
• CPC Class Codes: B01J 29/763 : CHA-type, e.g. Chabazite, LZ-218
• CPC Class Codes: B01J 35/19 : Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/56 : Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
• CPC Class Codes: B01J 35/657 : larger than 1000 nm
• CPC Class Codes: B01J 37/024 : Multiple impregnation or coating
• CPC Class Codes: F01N 2370/04 : Zeolitic material
• CPC Class Codes: F01N 3/035 : with catalytic reactors , e.g. catalysed diesel particulate filters
• CPC Class Codes: F01N 3/2066 : Selective catalytic reduction [SCR]
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

Provided are multi-zone catalyst articles, methods of manufacturing multi-zone catalyst articles, and methods for controlling emissions in diesel engine exhaust streams with multi-zone catalyst articles, where the emission treatment system of various embodiments effectively treats diesel engine exhaust with a single multi-zone catalyst article.

Claims

1. A catalyzed particulate filter comprising:

a plurality of porous walls extending longitudinally to form a plurality of parallel passages extending from an inlet end to an outlet end, wherein a quantity of the passages are inlet passages that are open at the inlet end and closed at the outlet end, and a quantity of passages are outlet passages that are closed at the inlet end and open at the outlet end;

a first coating permeating through at least a portion of the porous walls of the particulate filter, wherein the length of porous wall permeated with the first coating is in the range of about 1% to about 80% of the wall length extending from the outlet end of the passages, and wherein the first coating is an oxidation catalyst comprising a platinum group metal; and

a second coating permeating through at least a portion of the porous walls of the particulate filter, wherein the length of porous wall permeated with the second coating is in the range of about 50% to about 100% of the wall length extending from the inlet end of the passages, and wherein the second coating comprises a first selective catalytic reduction catalyst.

2. The catalyzed particulate filter of claim 1, wherein the first selective catalytic reduction catalyst is a zeolitic framework material promoted with a metal selected from Cu, Fe, Co, Ni, La, Ce, Mn, V, Ag, and combinations thereof.

3. The catalyzed particulate filter of claim 1, wherein the second coating permeates the porous walls of the particulate filter over about 90-100% the entire length of the porous walls of the particulate filter, and the first coating is intermingled with the second coating over about 1% to about 80% of the wall length extending from the outlet end of the passages.

4. The catalyzed particulate filter of claim 3, wherein the first selective catalytic reduction catalyst comprises a molecular sieve promoted with a base metal, and wherein the length of the porous walls permeated only with the second coating forms a first catalytic zone, and the length of the porous walls permeated with both the first coating and second coating forms a second catalytic zone, wherein the oxidation catalyst intermingles with the first selective catalytic reduction catalyst in the second catalytic zone.

5. The catalyzed particulate filter of claim 4, wherein the platinum group metal loading in the second catalytic zone is in the range of about 0.1 g/ft³ to about 50 g/ft³.

6. The catalyzed particulate filter of claim 1, wherein the length of porous wall permeated with the second coating is in the range of about 50% to about 80% of the wall length extending from the inlet end of the passages;

wherein the length of porous wall that is permeated with the first coating but not permeated with the second coating is in the range of about 20% to about 50% of the wall length extending from the outlet end of the passages; and

wherein the length of porous wall permeated with the second coating and having an overlapping first coating is in the range of about 5% to about 60% of the wall length, where the first coating is coated onto the surface of the overlapping portion of the porous wall permeated with the second coating.

7. The catalyzed particulate filter of claim 6, which further comprises a third coating that permeates through a portion of the porous walls of the particulate filter in the range of about 20% to about 80% of the wall length from the outlet end, wherein the third coating comprises a second selective reduction catalyst;

wherein the length of the porous walls permeated only with the second coating forms a first catalytic zone of a first SCR catalyst, the length of the porous walls permeated with the second coating and coated on the surface with the first coating forms a second catalytic zone of the first SCR catalyst and AMOx catalyst, and the length of the porous walls permeated with both the first coating and third coating forms a third catalytic zone of the second SCR catalyst and AMOx catalyst.

8. The catalyzed particulate filter of claim 6, which further comprises a third coating that permeates through a portion of the porous walls of the particulate filter in the range of about 20% to about 80% of the wall length from the outlet end, wherein the third coating comprises a second selective reduction catalyst;

wherein the length of the porous walls permeated only with the second coating forms a first catalytic zone of a first SCR catalyst, the length of the porous walls permeated with the second coating and the third coating forms a second catalytic zone of the first SCR catalyst and the second SCR catalyst, and the length of the porous walls permeated with both the first coating and third coating forms a third catalytic zone of the second SCR catalyst and AMOx catalyst.

9. The catalyzed particulate filter of claim 1, wherein the length of porous wall permeated with the second coating is in the range of about 95% to about 100% of the wall length extending from the inlet end of the passages;

wherein the length of porous wall that is permeated with the first coating but not permeated with the second coating is in the range of about 0% to about 5% of the wall length extending from the outlet end of the passages;

wherein the length of porous wall permeated with the second coating and having an overlapping first coating is in the range of about 5% to about 75% of the wall length, where the first coating is coated onto the surface of the overlapping portion of the porous wall permeated with the second coating; and

which further comprises a third coating that permeates through the portion of the porous walls of the particulate filter not permeated with the second coating, wherein the third coating comprises a second selective reduction catalyst, and the third coating is coated onto the surface of the overlapping portion of the porous wall permeated with the second coating.

10. The catalyzed particulate filter of claim 9, wherein the length of the porous wall coated on the surface with the first coating and the third coating is about the same.

11. The catalyzed particulate filter of claim 9, which further comprises a plug coating on the outlet side of the closed outlet end of the inlet passages, wherein the plug coating comprises a platinum group metal.

12. The catalyzed particulate filter of claim 1,

wherein the porosity of the porous walls is in the range of about 40% to about 75%, and the mean pore size of the porous walls is in the range of about 10 μ

m to about 30 μ

m;

and the first selective catalytic reduction catalyst comprises a copper or iron promoted CHA structure type molecular sieve.

13. The catalyzed particulate filter of claim 1, which further comprises a third coating that permeates through the portion of the porous walls of the particulate filter in the range of about 20% to about 80% of the wall length from the outlet end;

wherein the third coating comprises a second selective reduction catalyst;

and wherein the length of the porous walls permeated only with the second coating forms a first catalytic zone of a first SCR catalyst, the length of the porous walls permeated with the second coating and the first coating forms a second catalytic zone of the first SCR catalyst and AMOx catalyst, and the length of the porous walls permeated with both the first coating and third coating forms a third catalytic zone of a second SCR catalyst and AMOx catalyst.

14. The catalyzed particulate filter of claim 13, wherein the third coating comprises a copper or iron promoted CHA structure type molecular sieve.

15. The catalyzed particulate filter of claim 13, wherein the length of porous wall permeated with the second coating is in the range of about 95% to about 100% of the wall length extending from the inlet end of the passages, the length of porous wall coated on the surface with the first coating is in the range of about 5% to about 50% of the wall length, and the third coating permeated through the portion of the porous walls of the particulate filter not permeated with the second coating and coated onto the surface of the porous wall in the range of about 1% to about 70% of the wall length, wherein at least a portion of the first coating on the surface of the porous wall is sandwiched between the second coating and a portion of the third coating.

16. A method of manufacturing a coated particulate filter, comprising:

introducing an oxidation catalyst comprising a plurality of particles into an outlet end of a plurality of parallel passages formed by a plurality of porous walls closed by a plug on an inlet end opposite the outlet end, wherein the particles of the oxidation catalyst permeates through at least a portion of the porous walls, and wherein the length of porous wall permeated with the oxidation catalyst is in the range of about 1% to about 80% of the wall length extending from the outlet end of the passages; and

introducing a first selective catalytic reduction catalyst comprising a plurality of particles into an inlet end of a plurality of parallel passages formed by a plurality of porous walls closed by a plug on an outlet side opposite the inlet side, wherein the particles of the first selective catalytic reduction catalyst permeates through the porous walls, and wherein the length of porous wall permeated with the particles of the first selective catalytic reduction catalyst is in the range of about 50% to about 100% of the wall length extending from the inlet end of the passages.

17. The method of claim 16, wherein the porosity of the porous walls is in the range of about 40% to about 70%, and the mean pore size of the porous walls is in the range of about 10 μ

m to about 30 μ

m;

wherein the oxidation catalyst further comprises at least one platinum group metal on the plurality of particles, and the plurality of particles of the oxidation catalyst have a composition of alumina, titania, zirconia, silica, silica/alumina, or a combination thereof; and

wherein the first selective catalytic reduction catalyst is a molecular sieve promoted with a metal selected from Cu, Fe, Co, Ni, La, V, Mo, W, Mn, Ce, Ag and combinations thereof.

18. The method of claim 16, wherein the first selective catalytic reduction catalyst is introduced into the inlet end of the plurality of parallel passages before the oxidation catalyst is introduced into the outlet end of the plurality of parallel passages, and the length of porous wall permeated with the first selective catalytic reduction catalyst is in the range of about 50% to about 80% of the wall length extending from the inlet end of the passages, the length of porous wall that is not permeated with the first selective catalytic reduction catalyst, but permeated with the oxidative catalyst, is in the range of about 20% to about 50% of the wall length extending from the outlet end of the passages, and the length of porous wall permeated with the first selective catalytic reduction catalyst and having an overlapping oxidation catalyst is in the range of about 5% to about 50% of the wall length, wherein the oxidation catalyst remains essentially on the surface of the overlapping portion of the porous wall without interspersing with the first selective catalytic reduction catalyst throughout the porous wall.

19. The method of claim 18, which further comprises introducing a second selective catalytic reduction catalyst comprising a plurality of particles comprising a copper or iron promoted CHA structure type molecular sieve into the outlet end of the plurality of parallel passages, wherein the second selective catalytic reduction catalyst permeates through the portion of the porous walls of the particulate filter not previously permeated with the first selective catalytic reduction catalyst, and wherein the first selective catalytic reduction catalysts comprises a copper or iron promoted CHA structure type molecular sieve.

20. The method of claim 16, wherein the length of porous wall permeated with the particles of the first selective catalytic reduction catalyst is in the range of about 95% to about 100% of the wall length extending from the inlet end of the passages, the length of porous wall coated on the surface with the particles of the oxidation catalyst is in the range of about 1% to about 80% of the wall length extending from the outlet end of the passages, and the second selective catalytic reduction catalyst is coated onto the porous walls in the range of about 1% to about 80% of the wall length extending from the outlet end of the passages, wherein the second selective catalytic reduction catalyst is coated onto the surfaces of the porous walls where the second selective catalytic reduction overlaps with the first selective catalytic reduction catalyst.

21. The method of claim 16, which further comprises coating a platinum group metal onto the filter such that it only covers the plug at the end of the outlet passages.

22. The method of claim 17, which further comprises:

impregnating the platinum group metal into the plurality of the alumina, Mania, zirconia, silica, silica/alumina, or a combination thereof particles by an incipient wetness technique followed by thermally treating the impregnated particles at a temperature of about 400°

C. to about 600°

C.,

wherein the loading of platinum group metal onto the length of porous wall permeated with the oxidation catalyst is in the range of about 0.1 g/ft³ to about 50 g/ft³.

23. The method of claim 22, wherein a copper or iron promoted CHA structure type molecular sieve is mixed with the plurality of platinum group metal impregnated particles to form a slurry, and the length of porous wall permeated with the slurry is in the range of about 10% to about 50% of the wall length extending from the outlet end of the passages.