Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions

• US 9,498,751 B2
• Filed: 01/16/2015
• Issued: 11/22/2016
• Est. Priority Date: 08/19/2011
• Status: Expired due to Fees

• Current Assignee: Umicore AG & Company KG (Umicore S.A.)
• Original Assignee: SDC Materials,Inc.
• Inventors: Yin, Qinghua, Qi, Xiwang, Biberger, Maximilian A., Sarkar, Jayashir
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US14/599,316
• Publication Number:
  US 20150217229A1
• Time in Patent Office: 676 Days
• Field of Search: 502/527.12
• US Class Current: 1/1
• CPC Class Codes: B01D 2255/1021 Platinum
• CPC Class Codes: B01D 2255/1023 Palladium
• 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 2255/9022 Two layers
• CPC Class Codes: B01D 2255/912 HC-storage component incorporated in the catalyst
• CPC Class Codes: B01D 2255/9155 Wall flow filters
• CPC Class Codes: B01D 2255/9202 Linear dimensions
• CPC Class Codes: B01D 2258/012 Diesel engines and lean burn 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 21/04 Alumina
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 23/44 Palladium
• CPC Class Codes: B01J 23/63 with rare earths or actinides
• CPC Class Codes: B01J 29/04 having base-exchange properties, e.g. crystalline zeolites B01J29/005 takes precedence
• CPC Class Codes: B01J 29/06 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• CPC Class Codes: B01J 29/068 Noble metals
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/23 : in a colloidal state
• CPC Class Codes: B01J 35/394 : Metal dispersion value, e.g. percentage or fraction
• CPC Class Codes: B01J 35/40 : characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• 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 37/0018 : Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/0213 : Preparation of the impregnating solution
• CPC Class Codes: B01J 37/0244 : Coatings comprising several layers
• CPC Class Codes: B01J 37/0246 : Coatings comprising a zeolite
• CPC Class Codes: B01J 37/16 : Reducing
• CPC Class Codes: B01J 37/349 : making use of flames, plasmas or lasers

Abstract

Disclosed are, inter alia, methods of forming coated substrates for use in catalytic converters, as well as washcoat compositions and methods suitable for using in preparation of the coated substrates, and the coated substrates formed thereby. The catalytic material is prepared by a plasma-based method, yielding catalytic material with a lower tendency to migrate on support at high temperatures, and thus less prone to catalyst aging after prolonged use. Also disclosed are catalytic converters using the coated substrates, which have favorable properties as compared to catalytic converters using catalysts deposited on substrates using solution chemistry. Also disclosed are exhaust treatment systems, and vehicles, such as diesel vehicles, particularly light-duty diesel vehicles, using catalytic converters and exhaust treatment systems using the coated substrates.

Claims

1. A coated substrate comprising:

a substrate;

a washcoat layer comprising zeolite particles; and

a washcoat layer comprising catalytically active particles;

wherein the catalytically active particles comprise plasma synthesized composite nano-particles bonded to micron-sized carrier particles, and the composite nano-particles comprise a support nano-particle and a catalytic nano-particle, the catalytic nano-particle comprising at least one platinum group metal.

2. The coated substrate of claim 1, wherein the washcoat layer comprising zeolite particles is formed on top of the washcoat layer comprising catalytically active particles.

3. The coated substrate of claim 1, wherein the washcoat layer comprising catalytically active particles is formed on top of the washcoat layer comprising zeolite particles.

4. The coated substrate of claim 1, wherein the catalytic nano-particles comprise platinum and palladium.

5. The coated substrate of claim 4, wherein the catalytic nano-particles comprise platinum and palladium in a weight ratio of 2:

1 platinum;

palladium.

6. The coated substrate of claim 1, wherein the support nano-particles have an average diameter of 10 nm to 20 nm.

7. The coated substrate of claim 1, wherein the catalytic nano-particles have an average diameter of between 1 nm and 5 nm.

8. The coated substrate of claim 1, wherein the washcoat layer comprising zeolite particles comprises metal-oxide particles and boehmite particles.

9. The coated substrate of claim 8, wherein the metal-oxide particles are aluminum-oxide particles.

10. The coated substrate of claim 8, wherein the zeolite particles comprise 60% to 80% by weight of the mixture of zeolite particles, metal-oxide particles, and boehmite particles in the washcoat layer comprising zeolite particles.

11. The coated substrate of claim 8, wherein the boehmite particles comprise 2% to 5% by weight of the mixture of zeolite particles, metal-oxide particles, and boehmite particles in the washcoat layer comprising zeolite particles.

12. The coated substrate of claim 8, wherein the metal-oxide particles comprise 15% to 38% by weight of the mixture of zeolite particles, metal-oxide particles, and boehmite particles in the washcoat layer comprising zeolite particles.

13. The coated substrate of claim 1, wherein the washcoat layer comprising zeolite particles does not include platinum group metals.

14. The coated substrate of claim 1, wherein the zeolite particles in the washcoat layer comprising zeolite particles each have a diameter of 0.2 microns to 8 microns.

15. The coated substrate of claim 1, wherein the washcoat layer comprising catalytically active particles further comprises boehmite particles and silica particles.

16. The coated substrate of claim 15, wherein the catalytically active particles comprise 35% to 95% by weight of the combination of the catalytically active particles, boehmite particles, and silica particles in the washcoat layer comprising catalytically active particles.

17. The coated substrate of claim 15, wherein the silica particles are present in an amount up to 20% by weight of the combination of the catalytically active particles, boehmite particles, and silica particles in the washcoat layer comprising catalytically active particles.

18. The coated substrate of claim 15, wherein the boehmite particles comprise 2% to 5% by weight of the combination of the catalytically active particles, the boehmite particles, and the silica particles in the washcoat layer comprising catalytically active particles.

19. The coated substrate of claim 15, wherein the washcoat layer comprising catalytically active particles comprises 92% by weight of the catalytically active particles, 3% by weight of the boehmite particles, and 5% by weight of the silica particles.

20. The coated substrate of claim 1, wherein the washcoat layer comprising catalytically active particles is substantially free of zeolites.

21. The coated substrate of claim 1, wherein the substrate comprises cordierite.

22. The coated substrate of claim 1, wherein the substrate comprises a honeycomb structure.

23. The coated substrate of claim 1, wherein the washcoat layer comprising zeolite particles has a thickness of 25 g/l to 90 g/l.

24. The coated substrate of claim 1, wherein the washcoat layer comprising catalytically active particles has a thickness of 50 g/l to 250 g/l.

25. The coated substrate of claim 1, further comprising a corner-fill layer deposited directly on the substrate.

26. The coated substrate of claim 1, wherein the coated substrate has a platinum group metal loading of 4 g/l or less and a light-off temperature for carbon monoxide at least 5°

C. lower than the light-off temperature of a substrate with the same platinum group metal loading deposited by wet-chemistry methods.

27. The coated substrate of claim 1, wherein the coated substrate has a platinum group metal loading of about 3.0 g/l to about 4.0 g/l.

28. The coated substrate of claim 1, said coated substrate having a platinum group metal loading of about 3.0 g/l to about 5.5 g/l, wherein after 125,000 miles of operation in a vehicular catalytic converter, the coated substrate has a light-off temperature for carbon monoxide at least 5 °

C. lower than a coated substrate prepared by depositing platinum group metals by wet chemical methods having the same platinum group metal loading after 125,000 miles of operation in a vehicular catalytic converter.

29. The coated substrate of claim 1, said coated substrate having a platinum group metal loading of about 3.0 g/l to about 5.5 g/l, wherein after aging for 16 hours at 800 °

C., the coated substrate has a light-off temperature for carbon monoxide at least 5 °

C. lower than a coated substrate prepared by depositing platinum group metals by wet chemical methods having the same platinum group metal loading after aging for 16 hours at 800 °

C.

30. A catalytic converter comprising a coated substrate according to claim 1.

31. An exhaust treatment system comprising a conduit for exhaust gas and a catalytic converter according to claim 30.

32. A diesel vehicle comprising a catalytic converter according to claim 31.

33. The diesel vehicle of claim 32, wherein said diesel vehicle is a light-duty diesel vehicle.

34. A method of treating an exhaust gas, comprising contacting the coated substrate of claim 1 with the exhaust gas.

35. A method of treating an exhaust gas, comprising contacting the coated substrate of claim 1 with the exhaust gas, wherein the substrate is housed within a catalytic converter configured to receive the exhaust gas.

36. A method of forming a coated substrate, the method comprising:

a) coating a substrate with a washcoat composition comprising zeolite particles; and

b) coating the substrate with a washcoat composition comprising catalytically active particles; and

wherein the catalytically active particles comprises plasma synthesized composite nano-particles which are bonded to micron-sized carrier particles, said composite nano-particles comprising a support nano-particle and a catalytic nano-particle, the catalytic nano-particle comprising at least one platinum group metal.

37. The method of claim 36, wherein coating the substrate with the washcoat layer comprising zeolite particles is performed before coating the substrate with the washcoat layer comprising catalytically active particles.

38. The method of claim 36, wherein coating the substrate with the washcoat layer comprising catalytically active particles is performed before coating the substrate with the washcoat layer comprising zeolite particles.

39. The method of claim 36, further comprising coating the substrate with a corner-fill washcoat prior to both step a) and step b).

40. The method of claim 36, wherein the washcoat composition comprising zeolite particles comprises a thickness of 25 g/l to 90 g/l.

41. The method of claim 36, wherein the washcoat composition comprising catalytically active particles comprises a thickness of 50 g/l to 250 g/l.

42. A washcoat composition comprising a solids content of:

35% to 95% by weight of catalytically active particles comprising plasma synthesized composite nano-particles bonded to micron-sized carrier particles, and the composite nano-particles comprise a support nano-particle and a catalytic nano-particle, the catalytic nano-particle comprising at least one platinum group metal; and

2% to 55% by weight of metal-oxide particles.

43. The washcoat composition of claim 42, further comprising up to 20% by weight of silica particles.

44. The washcoat composition of claim 42, wherein the metal oxide particles are aluminum oxide particles.

45. The washcoat composition of claim 42, wherein the solids are suspended in an aqueous medium at a pH between 3 and 5.

46. The washcoat composition of claim 42, said washcoat composition being characterized by being substantially free of zeolites.

47. The washcoat composition of claim 42, wherein said catalytically active particles comprise 92% by weight of the solids content.

48. The washcoat composition of claim 42, wherein said at least one platinum group metal comprises platinum and palladium in a 2:

1 Pt/Pd weight/weight ratio.

49. The washcoat composition of claim 42, further comprising 1% to 10% by weight of boehmite particles.

50. A method of forming a coated substrate, the method comprising:

a) coating a substrate with a washcoat composition comprising zeolite particles; and

b) coating the substrate with a washcoat composition containing catalytically active particles according to claim 42.

51. The method of claim 50, wherein coating the substrate with the washcoat layer comprising zeolite particles is performed before coating the substrate with the washcoat layer comprising catalytically active particles.

52. The method of claim 50, wherein coating the substrate with the washcoat layer comprising catalytically active particles is performed before coating the substrate with the washcoat layer comprising zeolite particles.

53. The method of claim 50, further comprising coating the substrate with a corner-fill washcoat prior to both step a) and step b).

54. The method of claim 50, wherein the washcoat composition comprising zeolite particles comprises a thickness of 25 g/l to 90 g/l.

55. The method of claim 50, wherein the washcoat composition comprising catalytically active particles comprises a thickness of 50 g/l to 250 g/l.

56. A coated substrate comprising a washcoat according to claim 42.

57. A coated substrate comprising a washcoat according to claim 42, further comprising a washcoat layer comprising zeolite particles.

58. A catalytic converter comprising a coated substrate according to claim 56.

59. An exhaust treatment system comprising a conduit for exhaust gas and a catalytic converter according to claim 58.

60. A diesel vehicle comprising a catalytic converter according to claim 58.

61. The diesel vehicle of claim 60, wherein the diesel vehicle is a light-duty diesel vehicle.