IP Library Granted Patent US 10,634,030
Granted Patent B2
US 10,634,030 · App. 15/532,751 · Granted Apr 28, 2020

Nitrous oxide removal catalysts for exhaust systems

Inventors: Yuejin Li (Edison, NJ); Xiaolai Zheng (Princeton Junction, NJ); Stanley Roth (Yardley, PA); Olga Gerlach (Ludwigshafen, DE); Andreas Sundermann (Bensheim, DE)
Assignee: BASF Corporation
F01N3/2066B01D53/9427B01J23/10B01J23/42B01J23/44B01J23/464B01J23/468B01J23/52B01J23/63B01J33/00B01J35/0006B01J35/04B01J35/1014B01J35/1019B01J35/1038B01J37/0201B01J37/0215B01J37/0244B01J37/0246B01J37/0248B01J37/08B01J37/082B01J37/088F01N3/0842F01N3/101F01N3/2839B01D53/945B01D53/9468B01D53/9472B01D2255/1025B01D2255/2065B01D2255/9022B01D2255/9032B01D2255/9155B01D2255/9205B01D2255/9207B01D2257/402B01J35/006B01J35/023B01J2523/00Y02C20/10Y02T10/22
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Quick Facts
Patent No.
US 10,634,030
App. No.
15/532,751
Granted
Apr 28, 2020
Kind
B2
Abstract

A nitrous oxide (N 2 O) removal catalyst composite is provided, comprising a N 2 O removal catalytic material on a substrate, the catalytic material comprising a rhodium (Rh) component supported on a ceria-based support, wherein the catalyst composite has a H 2 -consumption peak of about 100° C. or less as measured by hydrogen temperature-programmed reduction (H 2 -TPR). Methods of making and using the same are also provided.

Claims (38)

1. A nitrous oxide (N 2 O) removal catalyst composite for an exhaust stream of an internal combustion engine comprising: a N 2 O removal catalytic material on a substrate, the catalytic material comprising a rhodium (Rh) component supported on a ceria-based support, wherein the catalytic material has a H 2 -consumption peak of about 100° C. or less as measured by hydrogen temperature-programmed reduction (H 2 -TPR) and is effective to decompose at least a portion of nitrous oxide (N 2 O) in the exhaust stream to nitrogen (N 2 ) and oxygen (O 2 ) or to reduce at least a portion of the N 2 O to N 2 and water, N 2 and carbon dioxide (CO 2 ), or N 2 , water, and CO 2 under conditions of the exhaust stream, and

wherein the ceria-based support comprises ceria in an amount in the range of about 56 to about 100% by weight of the support on an oxide basis.

2. The N 2 O removal catalyst composite of claim 1 , wherein the H 2 -consumption peak after aging at 750° C. for 20 hours with 10 volume % water in air occurs at a lower temperature than the temperature of the H 2 -consumption peak of fresh catalytic material.

3. The N 2 O removal catalyst composite of claim 1 , wherein N 2 O removal activity of the catalytic material after aging at 750° C. for 20 hours with 10 volume % water is higher than N 2 O removal activity of fresh catalytic material.

4. The N 2 O removal catalyst composite of claim 1 , wherein the ceria-based support maintains about 90 to about 100% of its pore volume after aging at 750° C. for 20 hours with 10 weight % water in air.

5. The N 2 O removal catalyst composite of claim 1 , wherein the ceria-based support comprises about 90 to about 100 weight % CeO 2 and has a pore volume that is at least about 0.20 cm 3 /g.

6. The N 2 O removal catalyst composite of claim 1 , wherein the ceria-based support comprises a fresh surface area that is in the range of about 40 to about 200 m 2 /g.

7. The N 2 O removal catalyst composite of claim 1 , wherein the ceria-based support comprises a surface area that is in the range of about 20 to about 140 m 2 /g after aging at 750° C. for 20 hours with 10 weight % water in air.

8. The N 2 O removal catalyst composite of claim 1 , wherein the ceria has a crystallite size in the range of about 3 to about 20 nm measured by x-ray diffraction (XRD).

9. The N 2 O removal catalyst composite of claim 1 , wherein the ceria-based support comprise: an x-ray diffraction crystallite size ratio of aged material to fresh material of about 2.5 or less, where aging is at 750° C. for 20 hours with 10% H 2 O in air.

10. The N 2 O removal catalyst composite of claim 1 , wherein the ceria-based support further comprises a promoter comprising yttria, samaria, gadolinia, zirconia, or silica.

11. The N 2 O removal catalyst composite of claim 1 , wherein the rhodium component is present on the support in an amount in the range of about 0.01 to about 5% by weight of the support.

12. The N 2 O removal catalyst composite of claim 1 , wherein the rhodium component is present in an amount of about 0.04 to about 3% by weight of the support.

13. The N 2 O removal catalyst composite of claim 1 , wherein the rhodium component has a crystallite size of less than about 5 nm.

14. The N 2 O removal catalyst composite of claim 1 , wherein the rhodium component is loaded on the substrate in an amount in the range of about 1 to about 105 g/ft 3 .

15. The N 2 O removal catalyst composite of claim 1 , wherein the catalytic material further comprises an additional metal component.

16. The N 2 O removal catalyst composite of claim 15 , wherein the additional metal component comprises platinum (Pt), palladium (Pd), silver (Au), copper (Cu), or combinations thereof.

17. The N 2 O removal catalyst composite of claim 15 , wherein the catalytic material further comprises a metal oxide for promoting the Rh and/or additional metal component.

18. The N 2 O removal catalyst composite of claim 17 , wherein the metal oxide comprises ceria, praseodymia, yttria, samaria, or gadolinia.

19. The N 2 O removal catalyst composite of claim 1 , wherein the substrate comprises a monolithic substrate.

20. The N 2 O removal catalyst composite of claim 1 , wherein the substrate comprises a wall-flow filter.

21. The N 2 O removal catalyst composite of claim 1 for an exhaust stream of an internal combustion engine comprising: a N 2 O removal catalytic material in a washcoat on a substrate, the catalytic material comprising a rhodium (Rh) component supported on a ceria-based support and is effective to convert nitrous oxide (N 2 O) under conditions of the exhaust stream, wherein the ceria-based support comprises:

about 90 to about 100 weight % CeO 2 ;

a pore volume that is in the range of about 0.20 to about 0.40 cm 3 /g;

a fresh surface area that is in the range of about 40 to about 200 m 2 /g; and

an aged surface area that is in the range of about 20 to about 140 m 2 /g after aging at 750° C. for 20 hours with 10 weight % water in air.

22. An emissions treatment system for treatment of an internal combustion engine exhaust stream including hydrocarbons, carbon monoxide, and nitrogen oxides, the emission treatment system comprising:

an exhaust conduit in fluid communication with the internal combustion engine via an exhaust manifold;

a treatment catalyst; and

the N 2 O removal catalyst composite of claim 1 .

23. The emissions treatment system of claim 22 , wherein the treatment catalyst comprises a precious metal on a high surface area refractory metal oxide support that is effective to oxidize hydrocarbons and/or carbon monoxide under conditions of the exhaust stream.

24. The emissions treatment system of claim 23 , wherein the treatment catalyst comprises a nitrogen oxides treatment catalyst selected from the group consisting of a three-way conversion (TWC) catalyst, a lean NOx trap (LNT), and a Selective Catalytic Reduction (SCR) catalyst.

25. The emissions treatment system of claim 24 , wherein the N 2 O removal catalyst composite is located downstream of the nitrogen oxides treatment catalyst.

26. The emissions treatment system of claim 24 , wherein the system is zoned and the nitrogen oxides treatment catalyst is in a front, upstream zone and the N 2 O removal catalyst composite is in a back, downstream zone.

27. The emissions treatment system of claim 24 , wherein the system is layered and the nitrogen oxides treatment catalyst is in an outer layer and the N 2 O removal catalytic material of the catalyst composite is in an inner layer.

28. The emissions treatment system of claim 24 , wherein the system is layered and the nitrogen oxides treatment catalyst is in an inner layer and the N 2 O removal catalytic material of the N 2 O catalyst composite is in an outer layer.

29. A method for treating exhaust gases comprising contacting a gaseous stream comprising hydrocarbons, carbon monoxide, and nitrogen oxides with the N 2 O removal catalyst composite of claim 1 .

30. The method of claim 29 , wherein N 2 O removal activity of the catalytic material after aging at 750° C. for 20 hours with 10 weight % water is higher than N 2 O removal activity of fresh catalytic material.

Assignments (4)
NUNC PRO TUNC ASSIGNMENT Recorded Aug 8, 2024
From: BASF CORPORATION
To: BASF MOBILE EMISSIONS CATALYSTS LLC
Reel/Frame 068518/0394 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 2, 2017
From: LI, YUEJIN; ZHENG, XIAOLAI; ROTH, STANLEY A.
To: BASF CORPORATION
Reel/Frame 042576/0799 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 2, 2017
From: GERLACH, OLGA; SUNDERMANN, ANDREAS
To: HTE GMBH
Reel/Frame 042576/0959 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 2, 2017
From: HTE GMBH
To: BASF CORPORATION
Reel/Frame 042577/0094 →
Continuity (2)
Provisional Application 62088888 · Dec 8, 2014
Related Publication 20170362984A1 · Dec 21, 2017