Zero Platinum Group Metal Catalysts

• US 20100240525A1
• Filed: 06/01/2010
• Published: 09/23/2010
• Est. Priority Date: 06/27/2008
• Status: Active Grant

• Current Assignee: ECS Holdings Limited, Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Original Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Inventors: Sakbodin, Mann, Hatfield, Randal, Pless, Jason, Ngo, Johnny, Golden, Stephen J.
• Granted Patent: US 8,685,352 B2
• Time in Patent Office: Days
• US Class Current: 502/65
• CPC Class Codes: B01D 2255/20707 Titanium
• CPC Class Codes: B01D 2255/20715 Zirconium
• CPC Class Codes: B01D 2255/20753 Nickel
• CPC Class Codes: B01D 2255/20761 Copper
• CPC Class Codes: B01D 2255/2092 Aluminium
• CPC Class Codes: B01D 2255/405 Spinels
• CPC Class Codes: B01D 2255/50 Zeolites
• CPC Class Codes: B01D 2255/908 O2-storage component incorporated in the catalyst
• CPC Class Codes: B01D 2257/30 Sulfur compounds
• CPC Class Codes: B01D 53/945 characterised by a specific catalyst
• CPC Class Codes: B01J 21/005 Spinels
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/08 of gallium, indium or thallium
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/83 with rare earths or actinides
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/17 Copper
• 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 2523/3725 : Neodymium
• CPC Class Codes: B01J 2523/48 : Zirconium
• CPC Class Codes: B01J 2523/72 : Manganese
• CPC Class Codes: B01J 35/0006 : Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/002 : Catalysts characterised by their physical properties
• CPC Class Codes: B01J 35/04 : Foraminous structures, sieves, grids, honeycombs
• CPC Class Codes: B01J 35/1014 : 10-100 m2/g
• CPC Class Codes: B01J 35/1038 : less than 0.5 ml/g
• CPC Class Codes: B01J 35/1042 : 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/19 : Catalysts containing parts with different compositions
• 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 35/613 : 10-100 m2/g
• CPC Class Codes: B01J 35/633 : less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 : 0.5-1.0 ml/g
• CPC Class Codes: B01J 37/0219 : the coating containing organic compounds
• CPC Class Codes: B01J 37/0244 : Coatings comprising several layers
• CPC Class Codes: Y02C 20/10 : of nitrous oxide (N2O)
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

The present invention pertains to catalyst systems for nitrogen oxide, carbon monoxide, hydrocarbon, and sulfur reactions that are free or substantially free of platinum group metals. The catalyst system of the present invention comprise a substrate and a washcoat, wherein the washcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof. The catalyst system may optionally have an overcoat, wherein the overcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof. The catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalysts, or mixtures thereof.

Claims

1. A catalyst system, comprising:

a substrate; and

a washcoat,

wherein the washcoat comprises at least one oxide solid,

wherein the oxide solid is selected from the group consisting of a carrier material oxide, a catalyst, and a mixture thereof,

wherein the catalyst system is substantially free of platinum group metals.

2. The catalyst system of claim 1, wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinet, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.

3. The catalyst system of claim 1, wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof.

4. The catalyst system of claim 2, wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof.

5. The catalyst system of claim 2, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

6. The catalyst system of claim 5, wherein the oxygen storage material comprises one or more selected from the group consisting of (a) a mixture of ceria and zirconia;

(b) a mixture of ceria, zirconia, and lanthanum; and

(c) a mixture of ceria, zirconia, neodymium, and praseodymium.

7. The catalyst system of claim 1, further comprising an overcoat comprising at least one oxide solid, wherein the overcoat oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof.

8. The catalyst system of claim 7, wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.

9. The catalyst system of claim 7, wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof.

10. The catalyst system of claim 8, wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof.

11. The catalyst system of claim 8, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

12. The catalyst system of claim 1, wherein the catalyst system is completely free of platinum group metals.

18. The catalyst system of claim 1 or 13 wherein the catalyst comprises at least one transition metal and at least one carrier material oxide,

wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese iron, cobalt, nickel, copper, niobium molybdenum, silver, and tungsten.

19. The catalyst system of claim 18, wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.

20. The catalyst system of claim 19, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

21. The catalyst system of claim 1 or 13, wherein the catalyst comprises copper and at least one carrier material oxide.

22. The catalyst system of claim 21, wherein the catalyst is about 5% to about 50% by weight.

31. The catalyst system of claim 2$, wherein the lanthanum aluminum oxide and oxygen storage material of the overcoat is present in a weight ratio of about 75 to about 25.

57. The catalyst system of claim 1 or 13, wherein the catalyst comprises at least one transition metal, at least one alkaline earth metal, cerium, and a carrier material oxide,

wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof, and

wherein the alkaline earth metal comprises one or more selected from the group consisting of magnesium, calcium, barium, strontium, and mixtures thereof.

58. The catalyst system of claim 57, wherein the alkaline earth metal and cerium are present in about 5% to about 50% by weight.

59. The catalyst system of claim 1 or 13, wherein the catalyst comprises at least one transition metal, at least one alkaline earth metal, and a carrier material oxide,

wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof, and

wherein the alkaline earth metal comprises one or more selected from the group consisting of magnesium, calcium, barium, strontium, and mixtures thereof.

60. The catalyst system of claim 59, wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, cobalt, and mixtures thereof.

61. The catalyst system of claim 59, wherein the alkaline earth metal comprises one or more selected from the group consisting of barium, strontium, and mixtures thereof.

62. The catalyst system of claim 59, wherein the alkaline earth metal and the transition metal are present in a molar ratio of about 1:

10 to 1;

1.

63. The catalyst system of claim 59, wherein the alkaline earth metal and the transition metal is about 2% to about 50% weight.

64. The catalyst system of claim 1 or 13, wherein the catalyst comprises at least one transition metal and a perovskite having the formula ABO₃,

wherein A comprises one or more selected from the group consisting of lanthanum, cerium, magnesium, calcium, barium, strontium, lanthanides, actinides, and mixtures thereof,

wherein B comprises one or more selected from the group consisting of iron, manganese, copper, nickel, cobalt, cerium, and mixtures thereof.

65. The catalyst system of claim 64, wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, cobalt, manganese, iron, chromium, niobium, molybdenum, tungsten, silver, and mixtures thereof.

66. The catalyst system of claim 65, wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, cobalt, and mixtures thereof.

67. The catalyst system of claim 64, wherein the transition metal is present in about 2% to about 30% by weight.

68. The catalyst system of claim 1 or 13, wherein the catalyst comprises a perovskite, at least one transition metal, and at least one carrier material oxide.

69. The catalyst system of claim 68, wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, and mixtures thereof.

70. The catalyst system of claim 68, wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.

71. The catalyst system of claim 70, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

72. The catalyst system of claim 68, wherein the perovskite and transition metal are present in about 5% to about 50% by weight.

73. The catalyst system of claim 1 or 13, wherein the catalyst comprises at least one transition metal and a spinel having the formula AB₂O₄,

wherein A comprises one or inure selected from the group consisting of aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, niobium, titanium, tin, and mixtures thereof, and

wherein B comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium nickel, copper, cobalt, iron, chromium, niobium, titanium, tin, and mixtures thereof,

wherein A and B are different.

74. The catalyst system of claim 73, wherein the transition metal comprises one or more selected from the group consisting of manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof.

75. The catalyst system of claim 73, wherein the spinel has the formula MgAl₂O₄.

76. The catalyst system of claim 73, wherein the transition metal is present in about 2% to about 30% by weight.

77. The catalyst system of claim 73, further comprising a carrier material oxide.

78. The catalyst system of claim 77, wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.

79. The catalyst system of claim 78, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

80. The catalyst system of claim 73, wherein the spinel and transition metal are present in about 5% to about 50% by weight.

81. The catalyst system of claim 1 or 13, wherein the catalyst comprises a mixed metal oxide and at least one transition metal,

wherein the mixed metal oxide comprises one or more selected from the group consisting of alkali metals, alkaline earth metals, lanthanides, actinides, and mixtures thereof.

82. The catalyst system of claim 81, wherein the mixed metal oxide comprises one or more selected from the group consisting of a spinel, a perovskite, a delafossite, lyonsite, a garnet, and a pyrochlore.

83. The catalyst system of claim 1 or 13, wherein the catalyst comprises a perovskite having the formula ABO₃,

wherein A comprises one or more selected from the group consisting lanthanum, lanthanides, actinides, cerium, magnesium, calcium, barium, strontium, and mixtures thereof, and

wherein B comprises at least one transition metal.

84. The catalyst system of claim 83, wherein the transition metal comprises one or more selected from the group consisting of iron, manganese, copper, nickel, cobalt, cerium, and mixtures thereof.

85. The catalyst system of claim 1 or 13, wherein the catalyst comprises a perovskite having the formula AB_a-xB_xMO_b,

wherein A comprises one or more selected from the group consisting lanthanum, lanthanides, actinides, cerium, magnesium, calcium, barium, strontium, and mixtures thereof,

wherein B comprises one or more transition metal,

wherein a is selected from the group consisting of 1 and 2,

wherein b is selected from the group consist of 3, when a is 1, and 4 when a is 2, and

wherein z is a number defined by 0.1≦

x<

0.7.

86. The catalyst system of claim 85, wherein the transition metal comprises one or more selected from the group consisting of iron, manganese, copper, nickel, cobalt, cerium, and mixtures thereof.

87. The catalyst system of claim 1 or 13, wherein the catalyst comprises a perovskite having the formula AMn_1-xCu_xO₃,

wherein A comprises one or more selected from the group consisting of lanthanum, cerium, barium, strontium, lanthanides, actinides, and mixtures thereof, and

wherein x is 0 to 1.

88. The catalyst system of claim 1 or 13, wherein the catalyst comprises a perovskite having the formula ACe_1-xCu_xO₃,

wherein A comprises one or more selected from the group consisting of barium, strontium, calcium, and mixtures thereof, and

wherein x is 0 to 1.

89. The catalyst system of claim 1 or 13, wherein the catalyst comprises a spinel having the formula AB₂O₄,

wherein A comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium nickel, copper, cobalt, iron, chromium, titanium, tin, and mixtures thereof;

and

wherein B comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, titanium, tin, and mixtures thereof,

wherein A and B are different.

90. The catalyst system of claim 89, further comprising a carrier material oxide.

91. The catalyst system of claim 90, wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.

92. The catalyst system of claim 91, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

93. The catalyst system of claim 89, wherein the spinel is present in the catalyst in about 5% to about 50% by weight.

94. The catalyst system of claim 1 or 13, wherein the catalyst comprises at least one zeolite and at least one transition metal.

95. The catalyst system of claim 94, wherein the zeolite comprises one or more selected from the group consisting of ZSM5, heulandite, chabazite, and mixtures thereof.

96. The catalyst system of claim 94, wherein the transition metal comprises one or more selected from the group consisting of chromium, gallium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof.

97. The catalyst system of claim 96, wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, gallium, cobalt, and mixtures thereof.

98. The catalyst system of claim 94, wherein the transition metal is present in about 3% to about 25% by weight.

13. A catalyst system, comprising:

a substrate;

a washcoat,

wherein the washcoat comprises one or more selected from the group consisting of a carrier material oxide, ceramic, and mixtures thereof; and

an overcoat,

wherein the overcoat comprises a catalyst,

wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and a mixture thereof, and

wherein the catalyst system is substantially free of platinum group metals.

14. The catalyst system of claim 13, further comprising one or more selected from the group consisting of a perovskite, a spinet, an oxygen storage material, alumina, and mixtures thereof.

15. The catalyst system of claim 14, further comprising one or more selected from the group consisting of a spinel, an oxygen storage material, alumina, and mixtures thereof.

16. The catalyst system of claim 15, further comprising one or more selected from the group consisting of a spinel, an oxygen storage material, alumina, and mixtures thereof.

17. The catalyst system of claim 15 or 16, further comprising, one or more selected from the group consisting of (a) a spinel and at least one oxygen storage material;

and (b) alumina and at least one oxygen storage material.

23. A catalyst system, comprising:

a substrate,

wherein the substrate comprises cordierite;

a washcoat,

wherein the washcoat comprises copper, a spinet, and at least one oxygen storage material,

wherein the spinel comprises magnesium aluminum oxide,

wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, and lanthanum; and

an overcoat,

wherein the overcoat comprises copper, a spinel, and at least one oxygen storage material,

wherein the spinel comprises magnesium aluminum oxide,

wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, neodymium, and praseodymium,

wherein the catalyst system is substantially free of platinum group metals.

24. The catalyst system of claim 23, wherein the aluminum oxide and oxygen storage material of the overcoat is present in a weight ratio of about 75 to about 25.

25. The catalyst system of claim 23, wherein the copper in the overcoat is about 5% to about 50% by weight.

26. The catalyst system of claim 25, wherein the copper in the overcoat is about 10% to about 16% by weight.

27. The catalyst system of claim 23, wherein the catalyst system is completely free of platinum group metals.

28. A catalyst system, comprising:

a substrate,

wherein the substrate comprises cordierite;

a washcoat,

wherein the washcoat comprises lanthanum aluminum oxide and at least one oxygen storage material; and

an overcoat,

wherein the overcoat comprises copper oxide, lanthanum aluminum oxide, and at least one oxygen storage material,

wherein the catalyst system is substantially free of platinum group metals.

29. The catalyst system of claim 28, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

30. The catalyst system of claim 28, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, neodymium, praseodymium, and mixtures thereof.

32. The catalyst system of claim 28, wherein the copper is present in about 5% to about 50% by weight.

33. The catalyst system of claim 28, wherein the aluminum oxide and the oxygen storage material of the overcoat is present in the overcoat in a weight ratio of about 75 to about 25.

34. The catalyst system of claim 28, wherein the catalyst system is completely free of platinum group metals.

35. A catalyst system, comprising:

a substrate;

a washcoat,

wherein the washcoat comprises tin aluminum oxide, copper, cerium, zirconium, lanthanum, and at least one oxygen storage material,

wherein the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium; and

an overcoat,

wherein the overcoat comprises aluminum, copper, and at least one oxygen storage material,

wherein the catalyst system is substantially free of platinum group metals.

36. The catalyst system of claim 35, wherein the oxygen storage material of the overcoat comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.

37. The catalyst system of claim 35, wherein the aluminum oxide and oxygen storage material are present in the washcoat in a weight ratio of 25:

75 to about 75;

25.

38. The catalyst system of claim 35, wherein the aluminum oxide and oxygen storage material are present in the washcoat in a weight ratio of about 60 to about 40.

39. The catalyst system of claim 35, wherein the aluminum and at least one oxygen storage material are present in the overcoat in a weight ratio of about 60 to about 40.

40. The catalyst system of claim 35, wherein the copper present in the overcoat is about 5% to about 20% by weight.

41. The catalyst system of claim 35, wherein the catalyst system is completely free of platinum group metals.

42. A catalyst system, comprising:

a substrate; and

a washcoat,

wherein the washcoat comprises copper, tin aluminum oxide, and at least one oxygen storage material,

wherein the catalyst system is substantially free of platinum group metals.

43. The catalyst system of claim 42, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, neodymium, and praseodymium, and mixtures thereof.

44. The catalyst system of claim 43, wherein the oxygen storage material comprises a mixture of cerium, zirconium, and lanthanum.

45. The catalyst system of claim 44, wherein the cerium, zirconium, and lanthanum is present in the washcoat in a weight ratio of about 60 to about 30 to about 10.

46. The catalyst system of claim 42, wherein the washcoat further comprises at least one transition metal.

47. The catalyst system of claim 42, wherein the copper present in the washcoat is about 5% to about 30% by weight.

48. The catalyst system of claim 42, wherein the catalyst system is completely free of platinum group metals.

49. A catalyst system, comprising:

a substrate; and

a washcoat,

wherein the washcoat comprises aluminum oxide, copper, and at least one oxygen storage material,

wherein the oxygen storage material comprises a mixture of cerium, zirconium, and lanthanum,

wherein the catalyst system is substantially free of platinum group metals.

50. The catalyst system of claim 49, wherein the aluminum oxide and the oxygen storage material are present in the washcoat in a weight ratio of about 60 to about 40.

51. The catalyst system of claim 49, wherein the copper present in the washcoat is about 5% to about 20% by weight.

52. The catalyst system of claim 49, wherein the washcoat further comprises one or more selected from the group consisting, of a transition metal, ceria, and a mixture thereof.

53. The catalyst system of claim 49, wherein the catalyst system is completely free of platinum group metals.

54. A catalyst system, comprising:

a substrate; and

a washcoat,

wherein the washcoat comprises at least one carrier material oxide and a perovskite,

wherein the perovskite comprises Ce_0.6La_0.4Mn_0.6Cu_0.4O₃,

wherein the catalyst system is substantially free of platinum group metals.

55. The catalyst system of claim 54, wherein the carrier material oxide comprises one or more oxygen storage material.

56. The catalyst system of claim 55, wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, neodymium, praseodymium, and mixtures thereof.

99-146. -146. (canceled)