Selective adsorbent material and its use

• US 7,416,655 B2
• Filed: 05/04/2005
• Issued: 08/26/2008
• Est. Priority Date: 10/10/2003
• Status: Expired due to Fees

• Current Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Original Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Inventors: Lozada y Cassou, Marcelo, López Salinas, Esteban, Ferrat Torres, Gerardo, Flores Ortiz, Luis Francisco, Ruiz Morales, Yosadara, Angeles Chávez, Carlos, Cortés Jacome, María Antonia, Toledo Antonio, José Antonio, Alvarez Ramírez, Fernando, Mosqueira Mondragon, Maria de Lourdes Araceli, Escobar Aguilar, Jose, Mora Vallejo, Rodolfo Juventino
• Primary Examiner(s): Griffin; Walter D.
• Assistant Examiner(s): NGUYEN, HUY TRAM
• Application Number:
  US11/121,179
• Publication Number:
  US 20050263441A1
• Time in Patent Office: 1,210 Days
• Field of Search: 208/208.R, 208/243, 208/244, 208/245, 208/246, 208/247, 208/248, 208/249, 208/254.R, 208/299, 208/295, 208/296, 208/297, 423/610, 423/608, 423/609, 977/734
• US Class Current: 208/249
• CPC Class Codes: B01J 20/0211 Compounds of Ti, Zr, Hf
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/28007 with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like carbon nanostructures B01J20/205
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 2220/42 Materials comprising a mixture of inorganic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: B01J 23/04 Alkali metals
• CPC Class Codes: B01J 23/70 of the iron group metals or copper
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.

Abstract

An adsorbent composition comprising a nanostructured titanium oxide material of the formula TiO_2-, where 0≦×≦1 with nanotubular and/or nanofibrilar morphology, high oxygen deficiency, having an orthorhombic JT crystalline phase described by at least one of the space groups 59 Pmmn, 63 Amma, 71Immm or 63 Bmmb, and comprising between 0 and 20 weight percent of a transition metal oxide is used for the selective adsorption of nitrogen compounds and/or sulfur compounds from light and intermediate petroleum fractions.

Claims

1. A process for the selective adsorption of nitrogen compounds and/or sulfur compounds from a hydrocarbon fraction, which comprises contacting said hydrocarbon fraction with an adsorbent comprising a nanostructured JT phase titanium oxide material of the formula TiO_2-x, where 0≦

×

≦

1, having an orthorhombic crystalline structure which is thermically stable and with a nanofibrilar and/or nanotubular morphology, constituted by piled structural layers, which are folded or rolled inwards into themselves, or formed from overlapped semitubes.

2. The process of claim 1, wherein said nanostructured titanium oxide material has a unit cell with orthorhombic symmetry, which is described by at least one of the space groups 59 Pmmn, 63 Amma, 71 Immm, or 63 Bmmb.

3. The process of claim 1, wherein said adsorbent additionally comprises a transition metal oxide promoter.

4. The process of claim 3, wherein said promoter is a Group IB, IIB, VI, VII or VIIIA metal oxide.

5. The process of claim 4, wherein said promoter is an oxide of cobalt or zinc.

6. The process of claim 1, wherein said hydrocarbon fraction is gasoline, diesel, primary straight run gas oil, FCC light naphtha or a FCC heavy naphtha.

7. The process of claim 6, wherein said process is conducted at a temperature between 0 and 150°

C. a pressure between 0.5 and 3.0 atm, an adsorbent/volume ratio of the hydrocarbon fraction to be treated between 0.01 and 0.5, and an adsorption time between 0.5 and 60 min.

8. The process of claim 6, wherein a gasoline fraction is treated said process is conducted at a pressure between 0.5 to 3 atm, a ratio of adsorbent mass/volume of treated hydrocarbon between 0.0125 and 0.2, an adsorption temperature between 10 and 40°

C., an adsorption time between 0.5 and 60 min, resulting in a percentage of nitrogen removal of 30 to 95%, and a percentage of sulfur removal of 5 to 72%.

9. The process of claim 6, wherein a diesel fraction is treated at a pressure between 0.5 to 3 atm, a ratio adsorbent mass/volume of treated hydrocarbon between 0.0125 and 0.2, adsorption temperature between 10 and 40°

C., adsorption time between 0.5 and 60 min, resulting in a percentage of nitrogen removal of 30 to 95%, and percentage of sulfur removal of 5 to 72%.

10. The process of claim 6, wherein a primary light straight run gas oil (SRGO) fraction is treated at a pressure between 0.5 to 3 atm, a ratio adsorbent mass/volume of treated hydrocarbon between 0.02 and 0.2, adsorption temperature between 5 and 60°

C., adsorption time between 0.5 and 60 min, resulting in a percentage of nitrogen removal of 30 to 95%, and a percentage of sulfur removal of 15 to 30%.

11. The process of claim 6, wherein a FCC light naphtha fraction is treated at a pressure between 0.5 to 3 atm, a ratio adsorbent mass/volume of treated hydrocarbon between 0.02 and 0.06, adsorption temperature between 20 and 30°

C., adsorption time between 0.5 and 60 min, resulting in a percentage of nitrogen removal of 85 to 95%, and a percentage of sulfur removal of 25 to 40%.

12. The process of claim 6, wherein a FCC heavy naphtha fraction is treated at a pressure between 0.5 to 3 atm, a ratio adsorbent mass/volume of treated hydrocarbon between 0.02 and 0.06, adsorption temperature between 20 and 45°

C., adsorption time between 0.5 and 60 min, resulting in a percentage of nitrogen removal of 85 to 95%, and percentage of sulfur removal of 15 to 20%.

13. The process of claim 6, wherein a FCC load is treated at a pressure between 0.5 to 3 atm, a ratio adsorbent mass/volume of treated hydrocarbon between 0.013 and 0.5, adsorption temperature between 20 and 100°

C., adsorption time between 4 and 30 min, resulting in a percentage of nitrogen removal of 35 to 85%.

14. The process of claim 4, wherein said adsorbent comprises between 1 and 20 weight percent of said promoter based on the total weight of said adsorbent.

15. The process of claim 2, wherein said nanostructured titanium oxide material has a unit cell with orthorhombic symmetry, which is described by the space group 59 Pmmn.

16. The process of claim 2, wherein said nanostructured titanium oxide material has a unit cell with orthorhombic symmetry, which is described by the space group 63 Amma

17. The process of claim 2, wherein said nanostructured titanium oxide material has a unit cell with orthorhombic symmetry, which is described by the space group 71 Immm.

18. The process of claim 2, wherein said nanostructured titanium oxide material has a unit cell with orthorhombic symmetry, which is described by the space group 63 Bmmb.

19. The process of claim 2, wherein said adsorbent comprises between 1 and 20 weight percent of said promoter based on the total weight of said adsorbent composition.

20. The process of claim 19, wherein said promoter is a Group IB, IIB, VI, VII or VIIIA metal oxide.

21. The process of claim 20, wherein said promoter is an oxide of Zn, Cu, Ni, Co, Fe, Ag, Mn, Cr, V, Mo, W, Co or Zn.

22. The process of claim 21, wherein said promoter is an oxide of Co or Zn.

23. The process of claim 19, wherein said composition is formed by a process including subjecting a hydrogen titanate and/or mixed sodium and hydrogen to ionic exchange with a Cu or a Zn oxide.

24. The process of claim 3, wherein in which the nanostructured titanium oxide material comprises between 99 weight percent and 80 weight percent of the total weight of said adsorbent.

25. The process of claim 1, wherein the nanostructured titanium oxide presents an specific superficial area in the range of 50 and 500 m2/g, and a pore distribution between 2 and 10 nm.

26. The process of claim 1, wherein the nanostructured titanium oxide material has an orthorhombic structure with a unit cell described by the spatial group 59 Pmmn, an X-ray peak about 10 degrees in the 2θ

scale (plane 200), and a number of structural layers between 1 and 50.

27. The process of claim 1, wherein the nanostructured titanium oxide presents oxygen vacancies represented by the formula:

TiO_2-x (where x=0 to

     1).

28. The process of claim 1, wherein said adsorbent comprising the nanostructured titanium oxide is in the form of particles, powders, tablets, extrudates, spheres or microspheres.