Modified carbide and oxycarbide containing catalysts and methods of making and using thereof

• US 6,936,565 B2
• Filed: 10/29/2001
• Issued: 08/30/2005
• Est. Priority Date: 01/12/1999
• Status: Expired due to Fees

• Current Assignee: Hyperion Catalysis International Incorporated
• Original Assignee: Hyperion Catalysis International Incorporated
• Inventors: Ma, Jun, Moy, David
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): Hailey, Patricia L.
• Application Number:
  US10/005,586
• Publication Number:
  US 20030008772A1
• Time in Patent Office: 1,401 Days
• Field of Search: 502/174, 502/177, 502/185, 502/180, 502/182, 502/527.14, 502/439, 4234471-4476, 501/87, 501/93, 428/40, 428/311.11, 428/312.2, 428/323, 428/367, 428/368
• US Class Current: 502/174
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 27/22 Carbides
• 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 37/24 Chlorinating
• CPC Class Codes: B01J 37/28 Phosphorising
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/34 Length
• CPC Class Codes: C01B 2202/36 Diameter
• CPC Class Codes: C01B 32/15 Nano-sized carbon materials
• CPC Class Codes: C01B 32/168 After-treatment
• CPC Class Codes: C01B 32/18 Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
• CPC Class Codes: C01B 32/907 Oxycarbides; Sulfocarbides; Mixture of carbides
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/13 Nanotubes
• CPC Class Codes: C01P 2004/50 Agglomerated particles
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2004/80 : Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2004/82 : two phases having the same anion, e.g. both oxidic phases
• CPC Class Codes: C01P 2006/10 : Solid density
• CPC Class Codes: C01P 2006/14 : Pore volume
• CPC Class Codes: C01P 2006/60 : Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C01P 2006/80 : Compositional purity
• CPC Class Codes: C30B 23/00 : Single-crystal growth by condensing evaporated or sublimed materials
• CPC Class Codes: C30B 29/605 : Products containing multiple oriented crystallites, e.g. columnar crystallites
• CPC Class Codes: D01F 11/122 : Oxygen, oxygen-generating compounds anode oxidising D01F11/16
• CPC Class Codes: D01F 9/12 : Carbon filaments; Apparatus specially adapted for the manufacture thereof
• CPC Class Codes: Y10S 977/788 : Of specified organic or carbon-based composition
• CPC Class Codes: Y10T 428/249962 : Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
• CPC Class Codes: Y10T 428/249967 : Inorganic matrix in void-containing component
• CPC Class Codes: Y10T 428/25 : Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/292 : In coating or impregnation

Abstract

Compositions including modified carbide-containing nanorods and/or modified oxycarbide-containing nanorods and/or modified carbon nanotubes bearing carbides and oxycarbides and methods of making the same are provided. Rigid porous structures including modified oxycarbide-containing nanorods and/or modified carbide containing nanorods and/or modified carbon nanotubes bearing modified carbides and oxycarbides and methods of making the same are also provided. The compositions and rigid porous structures of the invention can be used either as catalyst and/or catalyst supports in fluid phase catalytic chemical reactions. Processes for making supported catalyst for selected fluid phase catalytic reactions are also provided.

Claims

1. A catalytic composition comprising:

a plurality of nanostructures selected from the group consisting of carbon nanotubes, carbide nanorods, and mixtures thereof, each having a substantially uniform diameter between 1 nm and 100 nm and a length to diameter ratio greater than 5, said nanostructures further including a metal compound selected from the group consisting of carbides and oxycarbides of a transition metal, rare earth metal or actinide, said composition having an ammonia desorption peak at a temperature greater than 100°

C.

2. The catalytic composition of claim 1, wherein said metal is selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium, molybdenum, vanadium and tungsten.

3. The catalytic composition of claim 1, wherein said nanostructures are substantially cylindrical, have graphitic layers concentric with their cylindrical axes and are substantially free of pyrolytically deposited carbon.

4. The catalytic composition of claim 1, wherein said composition includes 10% to 95% carbides by weight thereof.

5. The catalytic composition of claim 4, wherein said composition includes 0.5% to 25% oxycarbides.

6. The catalytic composition of claim 1, wherein said catalytic composition is bifunctional.

7. A catalytic composition comprising:

a plurality of nanostructures selected from the group consisting of carbon nanotubes, carbide nanorods, and mixtures thereof, each having a substantially uniform diameter between 1 nm and 100 nm and a length to diameter ratio greater than 5, said nanostructures further including a metal compound selected from the group consisting of carbides and oxycarbides of a transition metal, rare earth metal or actinide, said nanostructures having been modified by an acidification treatment.

8. The catalytic composition of claim 7, wherein said metal is selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium, molybdenum, vanadium and tungsten.

9. The catalytic composition of claim 7, wherein said acidification treatment is treatment with an acidifying compound.

10. The catalytic composition of claim 9, wherein said acidifying compound includes an element selected from the group consisting of bromine, chlorine, fluorine, iodine, nitrogen, phosphorus, oxygen, sulfur and any combination thereof.

11. The catalytic composition of claim 10, wherein said acidification treatment is selected from the group consisting of halogenation, chlorination, nitrogenation, oxygenation, and phosphorylation.

12. The catalytic composition of claim 7, wherein said nanostructures are substantially cylindrical, have graphitic layers concentric with their cylindrical axes and are substantially free of pyrolytically deposited carbon.

13. The catalytic composition of claim 7, wherein said composition includes 10% to 95% carbides by weight thereof.

14. The catalytic composition of claim 13, wherein said composition further includes 0.5% o 25% oxycarbides.

15. The catalytic composition of claim 7, wherein said catalytic composition is bifunctional.

16. A catalytic composition comprising:

(a) a rigid porous structure formed from a plurality of nanostructures selected from the group consisting of carbon nanotubes, carbide nanorods, and mixtures thereof, each having a substantially uniform diameter between 1 nm and 100 nm and a length to diameter ratio greater than 5, said nanostructures further including a metal compound selected from the group consisting of carbides and oxycarbides of a transition metal, rare earth metal or actinide, said rigid porous structure including a plurality of interstitial spaces between said nanostructures; and

(b) a solid acid in said interstitial spaces.

17. The catalytic composition of claim 16, wherein said metal is selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium, molybdenum, vanadium and tungsten.

18. The catalytic composition of claim 16, wherein said nanostructures are substantially cylindrical, have graphitic layers concentric with their cylindrical axes and are substantially free of pyrolytically deposited carbon.

19. The catalytic composition of claim 16, wherein said solid acid is a compound containing an element selected from the group consisting of aluminum and zirconium.

20. The catalytic composition of claim 19, wherein said solid acid is a compound containing aluminum and the solid acid has been chlorinated, sulfated, or phosphated.

21. The catalytic composition of claim 19, wherein said solid acid is a compound containing zirconium and the solid acid has been chlorinated, sulfated, or phosphated.

22. The catalytic composition of claim 16, wherein said rigid porous structure has a density greater than about 0.5 gm/cm³ and a porosity greater than about 0.8 cc/gm.

23. The catalytic composition of claim 22, wherein said rigid porous structure is substantially free of micropores and has a crush strength greater than about 1 lb/in².

24. The catalytic composition of claim 16, wherein said composition includes 10% to 95% carbides by weight thereof.

25. The catalytic composition of claim 24, wherein said composition includes 0.5% to 25% oxycarbides.

26. The catalytic composition of claim 16, wherein said composition is bifunctional.

27. A process of preparing a catalytic composition for conducting a fluid phase catalytic reaction comprising the step of:

acidifying a plurality of nanostructures selected from the group consisting of carbon nanotubes, carbide nanorods, and mixtures thereof, each having a substantially uniform diameter between 1 nm and 100 nm and a length to diameter ratio greater than 5, said nanostructures further including a metal compound selected from the group consisting of carbides and oxycarbides of a transition metal, rare earth metal or actinide.

28. The process of claim 27, wherein acidifying said nanostructures comprises using an acidifying compound containing an element selected from the group consisting of bromine, chlorine, fluorine, iodine, nitrogen, phosphorus, sulfur, oxygen and mixtures thereof.

29. The process of claim 28, wherein acidifying said nanostructures further comprises placing said nanostructures in a reactor;

and drying said nanostructures.

30. The process of claim 29, wherein acidifying said nanostructures further comprises passivating the plurality of nanostructures with oxygen.

31. The process of claim 27, wherein acidifying said nanostructures is achieved by chlorination, nitration, sulfation, or phosphorylation.

32. A process of preparing a catalytic composition for conducting a fluid phase catalytic reaction comprising the step of:

incorporating a solid acid within the plurality of interstitial spaces within a composition including a plurality of nanostructures selected from the group consisting of carbon nanotubes, carbide nanorods, and mixtures thereof, each having a substantially uniform diameter between 1 nm and 100 nm and a length to diameter ratio greater than 5, said nanostructures further including a metal compound selected from the group consisting of carbides and oxycarbides of a transition metal, rare earth metal or actinide.

33. The process of claim 32, further comprising passivating said composition with oxygen.

34. The process of claim 32, wherein said solid acid is a compound containing an element selected from the group consisting of aluminum and zirconium.

35. The process of claim 34, wherein said solid acid is a compound containing aluminum and said solid acid has been chlorinated, sulfated, or phosphated.

36. The process of claim 34, wherein said solid acid is a compound containing zirconium and said solid acid has been chlorinated, sulfated, or phosphated.