Method of controlling emissions from a diesel cycle internal combustion engine with perovskite-type metal oxide compounds

• US 20060081922A1
• Filed: 09/20/2005
• Published: 04/20/2006
• Est. Priority Date: 04/10/1996
• Status: Active Grant

• Current Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Original Assignee: Catalyst Health Solutions Incorporated (UnitedHealth Group Incorporated)
• Inventors: Golden, Stephen J.
• Granted Patent: US 7,514,055 B2
• Time in Patent Office: Days
• US Class Current: 257/335
• 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 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 2523/25 Barium
• 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 2523/67 Chromium
• CPC Class Codes: B01J 2523/72 Manganese
• CPC Class Codes: B01J 2523/821 Ruthenium
• CPC Class Codes: B01J 2523/822 Rhodium
• CPC Class Codes: B01J 2523/824 Palladium
• CPC Class Codes: B01J 2523/828 : Platinum
• CPC Class Codes: B01J 2523/842 : Iron
• CPC Class Codes: B01J 2523/845 : Cobalt
• CPC Class Codes: B01J 2523/847 : Nickel
• CPC Class Codes: F01N 2370/02 : used in catalytic reactors
• CPC Class Codes: F01N 2510/06 : for exhaust purification, e.g. catalytic reaction
• CPC Class Codes: F01N 2610/02 : the substance being ammonia or urea
• CPC Class Codes: F01N 3/206 : Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents F01N3/2066 takes precedence
• CPC Class Codes: F01N 3/281 : Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
• CPC Class Codes: F01N 3/2828 : Ceramic multi-channel monoliths, e.g. honeycombs
• CPC Class Codes: Y02A 50/20 : Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies
• CPC Class Codes: Y10S 502/525 : Perovskite

Abstract

Methods of controlling emissions from a diesel engine are provided. The method includes contacting the emissions with a perovskite-type catalyst consisting essentially of a metal oxide composition represented by the general formula A_a-xB_xMO_b, in which A is a mixture 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 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 perovskite-type catalyst may be used to oxidize hydrocarbons and carbon monoxide and to control particulate emissions in the diesel exhaust.

Claims

1-20. -20. (canceled)

21. A method of controlling gaseous emissions from Diesel cycle internal combustion engines, said method comprising contacting the gaseous emissions from the Diesel cycle internal combustion engine with a perovskite-type catalyst consisting essentially of a metal oxide composition represented by the general formula:

A_a-xB_xMO_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.

22. The method of claim 21, wherein A comprises elements selected from the group consisting of lanthanides having an atomic number of from 57 to 71.

23. The method of claim 21, wherein B is selected from the group consisting of Ca, Sr, and K.

24. The method of claim 21, wherein M is selected from the group consisting of Fe, Mn, Co, Ni, Ru, Cr, and mixtures thereof.

25. The method of claim 21, wherein the perovskite-type catalyst is selected from the group consisting of Ln_0.6Ca_0.4Co_0.3, Ln_0.83Sr_0.17MnO₃, Ln_0.7Sr_0.3CrO₃, Ln_0.6Ca_0.4Fe_0.8Mn_0.2O₃, Ln_0.8Sr_0.2Mn_0.9Ni_0.04Ru_0.06O₃, Ln_0.8K_0.2Mn_0.95Ru_0.05O₃, Ln_0.7Sr_0.3Cr_0.95Ru_0.05O₃, LnNiO₃, Ln₂(Cu_0.6Co_0.2Ni_0.2)O₄, Ln_0.6Ca_0.4Fe_0.8Mn_0.2O₃, Ln_0.8Sr_0.2Mn_0.9Ni_0.04Pd_0.06O₃, Ln_0.7Sr_0.3Mn_0.9Ni_0.04Ru_0.06O₃, LnMn_0.5Cu_0.5O₃, LnMn_0.8Ni_0.10Cu_0.10O₃, Ln_0.7Sr_0.3Mn_0.9Pd_0.1O₃, Ln_0.5Sr_0.5Mn_0.9Pd_0.1O₃, Ln_0.8Sr_0.2MnO₃, Ln_0.5Sr_0.5Mn_0.98Pd_0.02O₃, Ln_0.8Sr_0.2Mn_0.96Pd_0.04O₃, Ln_0.5Sr_0.5Mn_0.95Pt_0.05O₃, Ln_0.8Sr_0.2Mn_0.92Ni_0.05Pd_0.03O₃, Ln_0.8Sr_0.2Mn_0.94Pt_0.05Rh_0.01O₃, Ln_0.8Ba_0.2Mn_0.94Pd_0.06O₃, Ln_0.5Sr_0.5Mn_0.98Rh_0.02O₃, Ln_0.8Sr_0.2Co_0.9Ru_0.1O₃, Ln_0.8Sr_0.2Mn_0.9Ru_0.1O₃, Ln_0.5Sr_0.5Mn_0.95Pd_0.05O₃, Ln_0.5Sr_0.5Mn_0.95Ru_0.05O₃, and Ln_0.5Sr_0.5MnO₃, where Ln is a mixture of lanthanides originally in the form of a single phase mixed lanthanide collected from bastnasite.

26. The method of claim 21, wherein said catalyst is supported on a structure.

27. The method of claim 26, wherein said structure is a honeycomb support.

28. The method of claim 27, wherein said honeycomb support is a ceramic honeycomb support or a metal honeycomb support.

29. The method of claim 26, wherein a carrier material or a mixture of carrier materials is deposited onto the support structure, thereby forming a washcoat on the surface of the support structure.

30. The method of claim 29, wherein a solution of salts of element A and salts or oxides of elements B and M is impregnated into said washcoat.

31. The method of claim 30, wherein the impregnated washcoat is dried and calcined to form the perovskite-type catalyst in the form of a dispersion.

32. The method of claim 21, wherein said method comprises oxidizing hydrocarbons in said gaseous emissions.

33. The method of claim 21 wherein said method comprises oxidizing carbon monoxide in said gaseous emissions.

34. The method of claim 21, wherein said method comprises removing nitrogen oxides in said gaseous emissions through selective catalytic reduction of said nitrogen oxides.

35. The method of claim 34, wherein the nitrogen oxides are reduced with ammonia.

36. The method of claim 34, wherein the nitrogen oxides are reduced with hydrocarbons.

37. A method of controlling particulate emissions from Diesel cycle internal combustion engines, said method comprising contacting the particulate emissions from the Diesel cycle internal combustion engine with a perovskite-type catalyst consisting essentially of a metal oxide composition represented by the general formula:

A_a-xB_xMO_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.

38. The method of claim 37, wherein said catalyst is supported on a structure.

39. The method of claim 38, wherein said structure is a honeycomb support.

40. The method of claim 37, further comprising oxidizing the particulates.