Perovskite-type metal oxide compounds and method for preparing the compounds

• US 5,939,354 A
• Filed: 04/10/1996
• Issued: 08/17/1999
• Est. Priority Date: 04/10/1996
• Status: Expired due to Term

• Current Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Original Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Inventors: Golden, Stephen J.
• Primary Examiner(s): Caldarola, Glenn
• Assistant Examiner(s): BULLOCK, IN SUK C
• Application Number:
  US08/630,603
• Time in Patent Office: 1,224 Days
• Field of Search: 502/525, 502/302, 502/303, 502/304, 502/306, 502/324, 502/326, 502/328
• US Class Current: 502/400
• CPC Class Codes: B01D 53/945 characterised by a specific catalyst
• 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 2523/13 Potassium
• CPC Class Codes: B01J 2523/17 Copper
• CPC Class Codes: B01J 2523/23 Calcium
• CPC Class Codes: B01J 2523/24 Strontium
• CPC Class Codes: B01J 2523/3706 Lanthanum
• CPC Class Codes: B01J 2523/67 Chromium
• CPC Class Codes: B01J 2523/72 Manganese
• CPC Class Codes: B01J 2523/821 Ruthenium
• CPC Class Codes: B01J 2523/842 Iron
• CPC Class Codes: B01J 2523/845 Cobalt
• CPC Class Codes: B01J 2523/847 Nickel
• CPC Class Codes: Y02T 10/12 Improving ICE efficiencies

Abstract

A perovskite-type catalyst consisting essentially of a metal oxide composition. The metal oxide composition is represented by the general formula A_a-x B_x M0_b, in which A is a mixture of elements originally in the form of single phase mixed lanthanides collected from Bastnasite; B is a divalent or monovalent cation; M is at least one element selected from the group consisting of elements of an atomic number of from 23 to 30, 40 to 51, and 73 to 80; a is 1 or 2; b is 3 when a is 1 or b is 4 when a is 2; and x is a number defined by 0≦x<0.7. Methods for preparing the perovskite-type catalyst are also described.

Claims

1. A perovskite-type catalyst consisting essentially of a metal oxide composition represented by the general formula:

space="preserve" listing-type="equation">A.sub.a-x B.sub.x M0.sub.b

wherein

A is a mixture of elements originally in the form of a single phase mixed lanthanide collected from bastnasite

B is a divalent or monovalent cation;

M is at least one element selected from the group consisting of elements of an atomic number of from 22 to 30, 40 to 51, and 73 to 80;

a is 1 or 2;

b is 3 when a is 1 or b is 4 when a is 2;

and x is a number defined by 0≦

x<

0.7.

2. The perovskite-type catalyst of claim 1, wherein said A comprises elements selected from the group consisting of lanthanides having an atomic number of from 57 to 71.

3. The perovskite-type catalyst of claim 1, wherein said single phase mixed lanthanide has a natural ratio of lanthanides.

4. The perovskite-type catalyst of claim 1, wherein said single phase mixed lanthanide has a modified ratio of lanthanides.

5. The perovskite-type catalyst of claim 1, wherein said single phase mixed lanthanide contains at least 4% of cerium oxide analyzed on a LnO basis.

6. The perovskite-type catalyst of claim 1, wherein said B is selected from a group consisting of Ca, Sr, and K cations.

7. The perovskite-type catalyst of claim 1, wherein M is selected from a group consisting of Fe, Mn, Co, Ni, Ru, Cr, and mixtures thereof.

8. The perovskite-type catalyst of claim 1, wherein said metal oxide compound is in the form of a pellet.

9. The perovskite-type catalyst of claim 1, wherein said metal oxide compound is in the form of a monolith.

10. The perovskite-type catalyst of claim 9, wherein said monolith is a honeycomb.

11. The perovskite-type catalyst of claim 1, wherein said metal oxide compound is in the form of an open cell foam.

12. The perovskite-type catalyst of claim 1, wherein said metal oxide compound is deposited on a carrier.

13. The perovskite-type catalyst of claim 12, wherein said carrier is a ceramic support.

14. The perovskite-type catalyst of claim 12, wherein said carrier is a ceramic honeycomb.

15. The perovskite-type catalyst of claim 1 having a general formula Ln_1-x A_x M0 ₃.

16. The perovskite-type catalyst of claim 15, wherein x is a number about 0.4 to 0.5.

17. The perovskite-type catalyst of claim 16 having a formula Ln₀.6 Ca₀.4 Co0₃.

18. The perovskite-type catalyst of claim 16 having a formula Ln₀.83 Sr₀.17 Mn0₃.

19. The perovskite-type catalyst of claim 16 having a formula Ln₀.7 Sr₀.3 Cro₃.

20. The perovskite-type catalyst of claim 16 having a formula Ln₀.6 Ca₀.4 Fe₀.8 Mn₀.2 O₃.

21. The perovskite-type catalyst of claim 16 having a formula Ln₀.8 Sr₀.2 Mn₀.9 Ni₀.04 Ru₀.06 O₃.

22. The perovskite-type catalyst of claim 16 having a formula Ln₀.8 K₀.2 Mn₀.95 Ru₀.05 O₃.

23. The perovskite-type catalyst of claim 16 having a formula Ln₀.7 Sr₀.3 Cr₀.95 Ru₀.05 O₃.

24. The perovskite-type catalyst of claim 16 having a formula LnNi0₃.

25. The perovskite-type catalyst of claim 1 having a formula A_2-x B_x M0₄.

26. The perovskite-type catalyst of claim 25 having a formula Ln₂ (Cu₀.6 Co₀.2 Ni₀.2)O₄.

27. A perovskite-type metal oxide compound represented by the general formula:

space="preserve" listing-type="equation">A.sub.a-x B.sub.x M0.sub.b

wherein

A is a mixture of elements originally in the form of a single phase mixed lanthanide collected from bastnasite

B is a divalent or monovalent cation;

M is at least one element selected from the group consisting of elements of an atomic number of from 22 to 30, 40 to 51, and 73 to 80;

a is 1 or 2;

b is 3 when a is 1 or b is 4 when a is 2;

and x is a number defined by 0≦

x<

0.7; and

wherein said perovskite-type metal oxide compound having a B-site, and containing Mn on said B-site.

28. The perovskite-type metal oxide compound of claim 27, wherein said A comprises elements selected from the group consisting of lanthanides of an atomic number of from 57 to 71.

29. The perovskite-type metal oxide compound of claim 27 showing giant magnetoresistance effect.

30. The perovskite-type metal oxide compound of claim 29 having a formula Ln₀.83 Sr₀.17 Mn0₃.

31. A method for preparing a perovskite-type catalyst consisting essential of a metal oxide composition having component elements represented by the general formula:

space="preserve" listing-type="equation">A.sub.a-x B.sub.x M0.sub.b

wherein

A comprises a mixture of elements selected from the group consisting of yttrium and lanthanides of an atomic number of from 57 to 71;

B is a divalent or a monovalent cation;

M is at least one element selected from the group consisting of elements of an atomic number of from 22 to 30, 40 to 51, and 73 to 80;

a is 1 or 2;

b is 3 when a is 1 or b is 4 when a is 2;

and x is a number defined by 0≦

x<

0.7;

the method comprising;

forming a homogeneous mixture of a single phase mixed lanthanide salt and respective salts, or oxides of elements B and M, wherein said single phase mixed lanthanide salt is collected from bastnasite; and

forming a perovskite-type metal oxide composition from said homogeneous mixture.

32. The method of claim 31, wherein said homogeneous mixture is formed by dissolving said single phase mixed lanthanide salt and said respective salts, or oxides of elements B and M in a solution.

33. The method of claim 31, wherein said homogeneous mixture is formed by grinding said single phase mixed lanthanide salt and said respective salts, or oxides of elements B and M together.

34. The method of claim 32, wherein said solution is water.

35. The method of claim 32 further comprising a step of adding acid to form a precipitate having a foam structure on heating, and calcining said precipitate to form said perovskite-type metal oxide composition.

36. The method of claim 35, wherein said acid is malic acid.

37. The method of claim 35, wherein said calcining step is carried out with periodic grinding and homogenizing to form a powder of said perovskite-type metal oxide composition.

38. The method of claim 33 further comprising a step of grinding an oxide of element M together with said precipitate to form a second mixture, and calcining said second mixture to form said perovskite-type metal oxide compound having multiple M elements.

39. The method of claim 33 further comprising a step of calcining said homogenous mixture with periodic grinding and homogenizing to form said powder of said metal oxide compound.

40. The method of claim 31 further comprising a step of forming said perovskite-type metal oxide compound into a pellet.

42. The method of claim 31, wherein said single phase lanthanide salt contains a natural ratio of lanthanides.

43. The method of claim 31, wherein said single phase lanthanide salt contains a modified ratio of lanthanides.

44. The method of claim 31, wherein said single phase lanthanide salt is collected from a bastnasite concentrate.

45. The method of claim 44, wherein said single phase lanthanide salt is lanthanide (Ln) carbonate having a natural ratio of lanthanides.

46. The method of claim 31, wherein said single phase lanthanide salt is collected from a La concentrate.

47. The method of claim 46, wherein said single phase lanthanide salt is selected from a group consisting of a mixed hydrated lanthanide carbonate, and a mixed hydrated lanthanide nitrate.

48. The method of claim 31, wherein said single phase lanthanide salt comprising at least 4% of cerium oxide analyzed on a LnO basis.

49. The method of claim 31, wherein said single phase lanthanide salt is selected from a group consisting of nitrates, carbonates, acetates, oxalates, or chlorides of lanthanide.

50. The method of claim 31, wherein said salts of elements B and M are selected from a group consisting of nitrates, carbonates, acetates, oxalates, or chlorides.

51. The method of claim 31 further comprising a step of forming said perovskite-type metal oxide compound into a monolithic body.

52. The method of claim 51, wherein said monolithic body is a honeycomb.

53. The method of claim 31 further comprising a step of forming said perovskite-type metal oxide compound into an open cell foam.

54. The method of claim 31 further comprising a step of forming said perovskite-type metal oxide compound into an open cell foam.

55. The method of claim 31 further comprising a step of depositing said perovskite-type metal oxide compound on a carrier.

56. The method of claim 55, wherein said carrier is a ceramic support.

57. The method of claim 55, wherein said carrier is a ceramic honeycomb.

41. The method of 40, wherein said pellet is formed by using uniaxial cold press.