Base metal catalyst and method of using same

• US 8,765,085 B2
• Filed: 04/22/2013
• Issued: 07/01/2014
• Est. Priority Date: 04/26/2012
• Status: Active Grant

• Current Assignee: BASF Corporation (BASF SE)
• Original Assignee: BASF Corporation (BASF SE)
• Inventors: Tran, Pascaline Harrison, Liu, Xinsheng, Liu, Ye, Galligan, Michael P., Zhang, Qinglin
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US13/867,182
• Publication Number:
  US 20130330258A1
• Time in Patent Office: 435 Days
• Field of Search: 502/66, 502/303, 502/304, 502/305, 502/324, 502/325, 502/345, 423/213.2, 602/99, 603/01
• US Class Current: 423/213.2
• CPC Class Codes: B01D 2255/2042 Barium
• CPC Class Codes: B01D 2255/2045 Calcium
• CPC Class Codes: B01D 2255/2047 Magnesium
• CPC Class Codes: B01D 2255/2061 Yttrium
• CPC Class Codes: B01D 2255/2063 Lanthanum
• CPC Class Codes: B01D 2255/2065 Cerium
• CPC Class Codes: B01D 2255/2066 Praseodymium
• CPC Class Codes: B01D 2255/20707 Titanium
• CPC Class Codes: B01D 2255/20715 Zirconium
• CPC Class Codes: B01D 2255/20723 Vanadium
• CPC Class Codes: B01D 2255/2073 Manganese
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2255/20746 Cobalt
• CPC Class Codes: B01D 2255/20753 Nickel
• CPC Class Codes: B01D 2255/20761 Copper
• CPC Class Codes: B01D 2255/20769 Molybdenum
• CPC Class Codes: B01D 2255/20776 Tungsten
• CPC Class Codes: B01D 2255/2092 Aluminium
• CPC Class Codes: B01D 2255/2096 Bismuth
• CPC Class Codes: B01D 2255/30 Silica
• CPC Class Codes: B01D 2255/405 : Spinels
• CPC Class Codes: B01D 2255/407 : Zr-Ce mixed oxides
• CPC Class Codes: B01D 2255/50 : Zeolites
• CPC Class Codes: B01D 2255/65 : Catalysts not containing noble metals
• CPC Class Codes: B01D 2255/908 : O2-storage component incorporated in the catalyst
• CPC Class Codes: B01D 2255/91 : NOx-storage component incorporated in the catalyst
• CPC Class Codes: B01D 2255/912 : HC-storage component incorporated in the catalyst
• CPC Class Codes: B01D 2257/404 : Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/502 : Carbon monoxide
• CPC Class Codes: B01D 2258/014 : Stoichiometric gasoline engines
• 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: B01J 2229/186 : not in framework positions
• CPC Class Codes: B01J 23/002 : Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/83 : with rare earths or actinides
• CPC Class Codes: B01J 23/8892 : Manganese
• CPC Class Codes: B01J 2523/00 : Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/17 : Copper
• CPC Class Codes: B01J 2523/31 : Aluminium
• CPC Class Codes: B01J 2523/36 : Yttrium
• CPC Class Codes: B01J 2523/3706 : Lanthanum
• CPC Class Codes: B01J 2523/3712 : Cerium
• CPC Class Codes: B01J 2523/3718 : Praseodymium
• CPC Class Codes: B01J 2523/48 : Zirconium
• CPC Class Codes: B01J 2523/72 : Manganese
• CPC Class Codes: B01J 2523/842 : Iron
• CPC Class Codes: B01J 2523/845 : Cobalt
• CPC Class Codes: B01J 2523/847 : Nickel
• CPC Class Codes: B01J 29/7065 : CHA-type, e.g. Chabazite, LZ-218
• CPC Class Codes: B01J 29/763 : CHA-type, e.g. Chabazite, LZ-218
• CPC Class Codes: B01J 29/783 : CHA-type, e.g. Chabazite, LZ-218
• CPC Class Codes: B01J 35/30 : characterised by their physical properties
• 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 37/0036 : Grinding
• CPC Class Codes: B01J 37/038 : to form slurries or suspensions, e.g. a washcoat
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

Aspects of the invention relate to a base metal catalyst composition effective to catalyze the abatement of hydrocarbons, carbon monoxide and nitrogen oxides under both rich and lean engine operating conditions comprising a support including at least 10% by weight of reducible ceria doped with up to about 60% by weight of one or more of oxides selected from the group Al, Pr, Sm, Zr, Y, Si, Ti and La; and a base metal oxide on the reducible ceria support, the base metal selected from one or more of Ni, Fe, Mn, Cu, Co, Ba, Mg, Ga, Ca, Sr, V, W, Bi and Mo, the base metal catalyst composition effective to promote a steam reforming reaction of hydrocarbons and a water gas shift reaction to provide H₂ as a reductant to abate NOx. Other aspects of the invention relate to methods of using and making such catalysts.

Claims

1. A base metal catalyst composition effective to catalyze the abatement of hydrocarbons, carbon monoxide and nitrogen oxides under both rich and lean engine operating conditions comprising

a support including at least 10% by weight of reducible ceria doped with up to about 60% by weight of one or more of oxides selected from the group Al, Pr, Sm, Zr, Y, Si, Ti and La;

and

a base metal oxide on the reducible ceria support, the base metal selected from one or more of Ni, Fe, Mn, Cu, Co, Ba, Mg, Ga, Ca, Sr, V, W, Bi and Mo, the base metal catalyst composition effective to promote a steam reforming reaction of hydrocarbons and a water gas shift reaction to provide H₂ as a reductant to abate NOx.

2. The catalyst composition of claim 1, wherein the kinetics of each reaction matches rich-lean cycles of engine operation dynamics.

3. The catalyst composition of claim 1, wherein the catalyst provides thermodynamically limiting oxidants during rich operation and reductants during lean operation and reaction kinetics needed for near complete conversion of HC, CO and NOx.

4. The catalyst composition of claim 1, wherein the support includes at least 35% by weight of reducible ceria.

5. The catalyst composition of claim 4, wherein the support includes up to about 99% by weight of reducible ceria.

6. The catalyst composition of claim 1, wherein the reducible ceria is doped with up to about 90% by weight of one or more oxides of Al, Pr, Sm, Zr, Y and La.

7. The catalyst composition of claim 1, wherein the base metal is selected from one or more of Ni, Mn, Co, Mo, Ga, Fe, Cu, Mg and Ba.

8. The catalyst composition of claim 7, wherein the base metal is selected from one or more of Ni, Mn, Co, Fe, and Cu.

9. The catalyst composition of claim 1, wherein the base metal oxide is present in an amount ranging from about 1 to about 30 wt %.

10. The catalyst composition of claim 1, wherein the catalyst comprises two base metals.

11. The catalyst composition of claim 1, wherein the catalyst comprises three base metals.

12. The catalyst composition of claim 1, wherein the oxide of one or more of Al, Pr, Sm, Zr, Y, Si, Ti and La is present in an amount ranging from about 1 to about 50 wt %.

13. The catalyst composition of claim 1, wherein the support comprises oxides of Zr, and Pr.

14. The catalyst composition of claim 1, wherein the support comprises oxides of Al.

15. The catalyst composition of claim 1, wherein the support comprises oxides of Zr, La and Y.

16. The catalyst composition of claim 1, wherein the support further comprises a zeolite having a chabazite crystal structure.

17. A method of treating a gas stream generated by a motorcycle, the method comprising:

contacting a gas stream containing hydrocarbons, carbon monoxide and nitrogen oxides and generated by a motorcycle under both rich and lean engine operating conditions with a base metal catalyst composition comprising

a support including at least 10% by weight of reducible ceria doped with up to about 60% by weight of one or more of oxides selected from the group Al, Pr, Sm, Zr, Y, Si, Ti and La; and

a base metal oxide on the reducible ceria support, the base metal selected from one or more of Ni, Fe, Mn, Cu, Co, Ba, Mg, Ga, Ca, Sr, V, W, Bi and Mo, the base metal catalyst composition effective to promote a steam reforming reaction of hydrocarbons and a water gas shift reaction to provide H₂ as a reductant to abate NOx,

thereby removing at least a part of the hydrocarbons, carbon monoxide and nitrogen oxides in gas stream.

18. The method of claim 17, wherein the catalyst provides thermodynamically limiting oxidants during rich operation and reductants during lean operation and reaction kinetics needed for near complete conversion of HC, CO and NOx.

19. The method of claim 17, wherein the base metal oxide is present in an amount ranging from about 1 to about 30 wt %.

20. The method of claim 17, wherein the support includes at least 35% by weight of reducible ceria.