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Delaminated microporous solid

Imported: 23 Feb '17 | Published: 22 Oct '02

Antonio Chica Lara, Urbano Diaz Morales, Vicente Fornes Segui, Avelino Corma Canos

USPTO - Utility Patents

Abstract

The invention concerns a microporous oxide material ITQ6, with a characteristic X-ray diffraction pattern, and surface areas for which microporous surface area may be of at least 20 m

2/g the external surface area may be at least 350 m

2/g and the total surface area may be at least 400 m

2/g. It may be made via preparation of gel, its hydrothermal treatment, and the treatment of the resulting material with a swelling solution followed by at least partial delamination e.g., by mechanical agitation or ultrasonics. The final oxide material is calcined and, in its acid form or combined with metals, especially noble metals, is useful as catalyst for the isomerization of n-butene to isobutene, or in dewaxing and isodewaxing processes and as a catalytic cracking catalyst or as an additive in FCC catalysts.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described with reference to the accompanying drawings, in which:

FIG. 1 is an X-ray diffraction pattern of PREITQ6;

FIG. 2 is an X-ray diffraction pattern of product 1;

FIG. 3 is an X-ray diffraction pattern of ITQ-6; and

FIG. 4 shows the results of analysis of reactor effluent (the square, circle and triangle symbols showing the conversion, summarization and cracking values, respectively).

Claims

1. An oxide material which in its calcined form has an X-ray diffraction pattern which includes the values shown in Table 3, and has micropores and surface area characteristics, determined by N

2 adsorption desorption, of a total surface area of at least 400 m

2g

−1 and an external surface area of at least 350 m

2g

−1.

2. An oxide material according to claim 1 wherein the total surface area is at least 450 m

2/g and an external surface area is at least 400 m

2/g.

3. An oxide material which in its calcined form has an X-ray diffraction pattern which includes the values shown in Table 3, and has surface area characteristics, determined by N

2 adsorption desorption, of a microporous surface area of at least 20 m

2g

−1 and an external surface area of at least 350 m

2g

−1.

4. An oxide material according to claim 3, wherein the microporous surface area is at least 50 m

2g

−1 and the external surface area is at least 400 m

2g

−1.

5. A material according to claim 1 comprising the oxides XO

2 and Y

2O

3, where X represents a tetravalent element and Y represents a trivalent element.

6. A material according to claim 5, where X represents at least one of silicon germanium, and titanium.

7. A material according to claim 5, where Y represents at least one trivalent element selected from the group consisting of aluminium, boron, iron, chromium, gallium and mixtures thereof.

8. A material according to claim 5, where X represents silicon and Y represents aluminium.

9. A material according to claim 5 wherein the molar ratio of XO

2 to Y

2O

3 is at least 5:1.

10. A material according to claim 5, in which the atomic ratio of X to Y is at least 5:1.

11. An oxide material according to claim 10, in which the atomic ratio of X to Y is greater than 10:1.

12. An oxide material according to claim 5, in which the atomic ratio of X to Y is within a range of between 30 and 500.

13. An oxide material according to claim 1 comprising the oxide XO

2, wherein X represents a tetravalent element.

14. An oxide material according to claim 1 whose micro porous surface area is 50-100 m

2/g and whose external surface area is 450 to 600 m

2/g.

15. A process for the preparation of an oxide material as claimed in claim 1, which comprises converting into said material a precursor laminar oxide material with an X-ray diffraction pattern shown in FIG. 1 with basal spacing and relative intensities summarized in Table 1.

16. A process according to claim 15 which comprises at least partially delaminating a bulked product of said precursor laminar material.

17. A process according to claim 16 wherein said partial delaminating is performed by mechanical agitation or ultrasonic treatment.

18. A process according to claim 16 wherein the bulked product has been obtained by dispersing said precursor laminar material in a bulking solution comprising an organic compound with a hydrocarbon chain comprising at least three carbon atoms and a proton acceptor group, and a compound capable of supplying hydroxide ion to the dispersion.

19. A process according to claim 18 wherein the precursor laminar material is dispersed in a bulking solution comprising cetyl trimethylammonium hydroxide and tetrapropylammonium hydroxide.

20. A process according to claim 15 wherein the precursor lamina oxide material has been obtained by crystallization from a synthesis mixture comprising a source of silica, optionally a source of aluminium, a salt of fluoride and hydrogen fluoride and 4-amino-2,2,6,6-tetramethylpiperidine and water.

21. A process according to claim 16 wherein at least partial delamination is followed by acid treatment.

22. An oxide material obtained by or obtainable by a process according to claim 15.

23. A catalytic composition, which comprises an oxide material as claimed in claim 1, and at least one transition metal.

24. A composition according to claim 23, which also comprises a support.

25. A composition according to claim 24 wherein the support is alumina, silica or silica/alumina.

26. A composition according to claim 23, wherein the metal has a hydrogenating effect.

27. A composition according to claim 23 wherein the metal is Pt, Pd, Ru, Ni, Co, Mo, V, W, Rh or a mixture of any of these metals.

28. A composition according to claim 27 wherein the metal is Pt.

29. A composition according to claim 27 wherein the metals are Ni and Mo.

30. A catalytic composition which comprises an oxide material as claimed in claim 14, and a matrix.

31. A composition according to claim 30 wherein the matrix is a refractory oxide.

32. A process for isodewaxing a hydrocarbon feed which comprises contacting said feed with a catalyst composition according to claim 23 in the presence of hydrogen at elevated temperature and pressure.

33. A process for catalytic isomerisation of n-alkenes to branched alkenes which comprises contacting said n-alkene with a composition according to claim 23 at elevated temperature.

34. A process for cracking hydrocarbons, which comprises contacting said hydrocarbon with a composition according to claim 23 at elevated temperature and pressure in the presence or absence of water vapour.