Spinel compositions and applications thereof

• US 9,511,358 B2
• Filed: 09/30/2014
• Issued: 12/06/2016
• Est. Priority Date: 11/26/2013
• Status: Active Grant

• Current Assignee: Clean Diesel Technologies, Inc.
• Original Assignee: Clean Diesel Technologies, Inc.
• Inventors: Nazarpoor, Zahra, Golden, Stephen J.
• Primary Examiner(s): VANOY, TIMOTHY C
• Application Number:
  US14/503,003
• Publication Number:
  US 20150148216A1
• Time in Patent Office: 798 Days
• US Class Current: 1/1
• CPC Class Codes: B01D 2255/405 Spinels
• 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 23/005 Spinels
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 23/56 Platinum group metals
• CPC Class Codes: B01J 23/626 with tin
• CPC Class Codes: B01J 23/63 with rare earths or actinides
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/8933 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 23/8986 with manganese, technetium or rhenium
• CPC Class Codes: B01J 29/068 Noble metals
• CPC Class Codes: B01J 37/0244 Coatings comprising several layers
• CPC Class Codes: C01B 13/0281 in getters
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/1041 Composition of the catalyst
• CPC Class Codes: C01B 2203/1094 Promotors or activators
• CPC Class Codes: C01B 3/40 characterised by the catalyst
• CPC Class Codes: C08K 3/00 Use of inorganic substances as compounding ingredients
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08L 23/02 : not modified by chemical after-treatment
• CPC Class Codes: H01M 4/00 : Electrodes
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies

Abstract

Spinels having a general formula of AB₂O₄, where A and B are a transition metal but not the same transition metal are disclosed. Spinel and spinel compositions of the application are useful in various applications and methods as further described.

Claims

1. A catalyst comprising a spinel having the general formula of AB₂O₄, wherein A and B are a transition metal, wherein A and B are not the same transition metal, and wherein A is selected from the group consisting of manganese (Mn), nickel (Ni), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and B is selected from the group consisting of iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).

2. The catalyst of claim 1, wherein the transition metal is selected from the group consisting of iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), etc.) and an “

other metal”

(i.e., aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and indium (In).

3. The catalyst of claim 1, wherein the spinel is rare-earth metal free.

4. The catalyst of claim 1, wherein the spinel further comprises a dopant.

5. The catalyst of claim 4, wherein the spinel has a general formula of A_i-xD_xB₂O₄, where D is the dopant.

6. The catalyst of claim 4, wherein the dopant is selected from the group consisting of vanadium, silver, palladium, ruthenium, rhodium, platinum, molybdenum, tin, calcium (Ca), strontium (Sr), barium (Ba), lithium (Li), titanium, lanthanum (La), samarium (Sm), gadolinium (Gd), yttrium (Y), neodymium (Nd), cerium (Ce), aluminum, gallium, magnesium, zirconium (Zr), and tungsten (W), and further wherein D is not the same metal as A or B.

7. The catalyst of claim 4, wherein the dopant is a low valence dopant.

8. The catalyst of claim 4, wherein the dopant is a high valence dopant.

9. The catalyst of claim 1, wherein the spinel is deposited on a substrate.

10. The catalyst of claim 9, wherein the substrate is a support oxide.

11. The catalyst of claim 10, wherein the support oxide is transition alumina, alpha alumina, titania, zeolite, silica, silicate, magnesium-silicate, silica-alumina, ceria, ceria-zirconia, lanthanide-doped ceria-zirconia, lanthanum doped alumina, and mixed metal oxide.

12. The catalyst of claim 11, wherein the mixed metal oxide is selected from the group consisting of fluorite, pyrochlore, perovskite, pseudo-brookite, lanthanide oxide, titanium oxide, silver oxide, and tin oxide.

13. The catalyst of claim 4, wherein the dopant is an aliovalent dopant.

14. A battery comprising an anode or cathode, wherein the anode or the cathode comprise an active ingredient comprising a spinel having the general formula of AB₂O₄, wherein A and B are each independently a transition metal, wherein A and B are not the same transition metal, and wherein A is selected from the group consisting of nickel (Ni), vanadium (V), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi) and indium (In), and B is selected from the group consisting of iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), vanadium (V), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Ti), lead (Pb), bismuth (Bi), and indium (In).

15. A method of cleaning emissions from a combustion engine comprising directing exhaust from a combustion engine through or flow over a catalyst comprising a spinel having the general formula of AB₂O₄, wherein A and B are each independently a transition metal, wherein A and B are not the same transition metal, and wherein A is selected from the group consisting of manganese (Mn), nickel (Ni), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and B is selected from the group consisting of iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).

33. The method of claim 15, wherein the catalyst is a second coated substrate downstream from a conventional PGM based catalyst.

34. The method of claim 15, wherein the catalyst is upstream from a conventional PGM based underfloor converter.

16. A polymeric material comprising a polymeric formulation and a spinel having the general formula of AB₂O₄, wherein A and B are each independently a transition metal, wherein A and B are not the same transition metal.

17. The polymeric material of claim 16 wherein the polymeric formulation comprises a polyolefin.

18. The polymeric material of claim 16 wherein the polymeric formulation comprises at least one of a polyethylene or a polypropylene.

19. The polymeric material of claim 18, wherein the polyethylene is low density polyethylene, linear low density polyethylene, high density polyethylene, or mixtures thereof.

20. The polymeric material of claim 16 wherein the polymeric formulation comprises ethylene-vinyl acetate copolymers, ethylene-ethylacrylate copolymers, ethylene-acrylic acid copolymers, polymethylmethacrylate mixtures of at least two of the foregoing, or mixtures thereof.

21. A method of generating hydrogen comprising reacting carbon monoxide and steam with a catalyst comprising a spinel having the general formula of AB₂O₄, wherein A and B are a transition metal, wherein A and B are not the same transition metal, and wherein A is selected from the group consisting of iron (Fe), manganese (Mn), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and indium (In), and B is selected from the group consisting of iron (Fe), manganese (Mn), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and indium (In).

22. The method of claim 21 further comprising capturing the hydrogen generated.

23. A method of generating hydrogen comprising reacting steam with a hydrocarbon in a reforming catalyst, wherein the reforming catalyst comprises a spinel having the general formula of AB₂O₄, wherein A and B are a transition metal, wherein A and B are not the same transition metal.

24. The method of claim 23, wherein the hydrocarbon is selected from the group consisting of methane, natural gas, methanol, and ethanol.

25. The method of claim 23, wherein said reacting is performed at temperatures at about 700°

C. to about 1100°

C.

26. A thermoelectric composition comprising a spinel and aliovalent dopant, wherein the spinel has an oxygen vacancy or cation defect, and wherein the spinel has the general formula of AB₂O₄, wherein A and B are a transition metal, wherein A and B are not the same transition metal, and wherein A is selected from the group consisting of iron (Fe), manganese (Mn), nickel (Ni) cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi) and B is selected from the group consisting of iron (Fe), manganese (Mn), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).

27. The thermoelectric composition of claim 26, wherein the aliovalent dopant is selected from the group consisting of niobium, cerium, praseodymium, calcium, strontium, barium, aluminum, tantalum, tungsten, and tin.

28. The thermoelectric composition of claim 26, wherein the dopant forms a second phase oxide on a surface of the spinel.

29. The thermoelectric composition of claim 28, wherein the spinel is Cu_xMn_3-xCe_xO₄.

30. A spinel composition comprising a) spinel having the general formula of AB₂O₄, wherein A and B are a transition metal, wherein A and B are not the same transition metal;

b) a binder; and

optionally, c) an additive, and wherein A is selected from the group consisting of manganese (Mn), nickel (Ni), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and B is selected from the group consisting of iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).

31. A honeycomb support comprising the spinel composition of claim 30 and a platinum group metal catalyst coating.

32. A honeycomb support comprising the spinel composition of claim 30 and an alumina based material.

35. An oxygen storage material comprising a spinel having the general formula of AB₂O₄, wherein A and B are a transition metal, wherein A and B are not the same transition metal.

36. The oxygen storage material of claim 35, wherein the oxygen storage material comprises about 10 to about 90 wt % of a catalytic coating.

37. A catalytic converter comprising

i) a spinel having the general formula of AB₂O₄, wherein A and B are a transition metal, and wherein A and B are not the same transition metal;

ii) a platinum group metal (PGM), and wherein A is selected from the group consisting of manganese (Mn), nickel (Ni), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), bismuth (Bi), and B is selected from the group consisting of iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), copper (Cu), vanadium (V), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), platinum (Pt), molybdenum (Mo), niobium (Nb), titanium (Ti), aluminum (Al), magnesium (Mg), gallium (Ga), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).

38. The catalytic converter of claim 37, wherein the spinel and the PGM component or layer is deposited or coated on a substrate.

39. The catalytic converter of claim 38, wherein the substrate is cordierite.

40. The catalytic converter of claim 37, wherein the platinum group metal is selected from the group consisting of platinum, palladium, and rhodium.

41. The catalytic converter of claim 37, wherein the catalytic converter is a single layer catalyst, wherein the spinel and the PGM component are inter-mixed.

42. The catalytic converter of claim 37, wherein the PGM component is supported on a carrier.

43. The catalytic converter of claim 42, wherein the carrier is selected from the group consisting of alumina, titania, zirconia, ceria, cerium-based OSM, tin oxide, and zeolite.

44. The catalytic converter of claim 37, wherein the catalytic converter is a double layer catalyst, wherein the spinel and the PGM are in separate, distinct layers.

45. The catalytic converter of claim 37, wherein the catalytic converter is a double layer catalyst, wherein a first layer comprises a first PGM and a first spinel, and a second layer comprises a second PGM and a second spinel.

46. The catalytic converter of claim 37, wherein the PGM is impregnated onto a surface of the spinel.

47. The catalytic converter of claim 37, wherein the PGM is coated on a surface of the spinel.

48. The catalytic converter of claim 38, wherein the substrate is zone-coated with the spinel and the PGM.

49. The catalytic converter of claim 48, wherein the zone-coated substrate is coated with a spinel in a first region and coated with a PGM in a second region, wherein the first region is not coated with a PGM and the second region is not coated with a spinel.

50. The catalytic converter of claim 48, wherein the zone-coated substrate is coated with a PGM on a spinel composition in a first region and coated with a spinel without PGM in a second region.