Hierarchically ordered crystalline microporous materials with long-range mesoporous order having hexagonal symmetry

Patent metadata

Field	Value
Publication number	US-12290799-B2
Application number	US-202217857503-A
Country	US
Kind code	B2
Filing date	Jul 5, 2022
Priority date	Jul 5, 2022
Publication date	May 6, 2025
Grant date	May 6, 2025

Abstract

A composition of matter is provided comprising hierarchically ordered crystalline microporous material having well-defined long-range mesoporous ordering of hexagonal symmetry. The composition possesses mesopores having walls of crystalline microporous material and a mass of mesostructure between mesopores of crystalline microporous material. Long-range ordering is defined by presence of secondary peaks in an X-ray diffraction (XRD) pattern and/or hexagonal symmetry observable by microscopy.

First claim

What is claimed is:

1. A composition of matter comprising hierarchically ordered crystalline microporous material having well-defined long-range mesoporous ordering of hexagonal symmetry comprising mesopores having walls of crystalline microporous material and a mass of mesostructure between mesopores of crystalline microporous material, wherein the long-range ordering is defined by presence of secondary peaks in an X-ray diffraction (XRD) pattern including peaks occurring at 20 angles less than about 6°, and whereby long-range mesoporous ordering of hexagonal symmetry is observable by microscopy including mesopore periodicity repeating over a length of greater than about 50 nm.

2. The composition of matter as in claim 1 , wherein the hexagonal mesophase possesses p6m, p6 mm or P63/mmc symmetry.

3. The composition of matter as in claim 1 , wherein the hexagonal mesophase possesses p6 mm symmetry and secondary peaks in XRD are present at (11) and/or (20) reflections.

4. The composition of matter as in claim 1 , wherein the hexagonal mesophase possesses p6 mm symmetry and long-range ordering is observable by microscopy viewing an electron beam perpendicular to mesopores down a zone axis or parallel to mesopores down a zone axis.

5. The composition of matter as in claim 1 , wherein said crystalline microporous material comprises a zeolite or zeolite-type material.

6. The composition of matter as in claim 1 , wherein said crystalline microporous material is a zeolite having a framework selected from the group consisting of AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA and MWW.

7. The composition of matter as in claim 1 , wherein said crystalline microporous material is a zeolite having FAU framework.

8. A composition of matter comprising hierarchically ordered crystalline microporous material having well-defined long-range mesoporous ordering of hexagonal symmetry comprising mesopores having walls of crystalline microporous material and a mass of mesostructure between mesopores of crystalline microporous material, wherein at least a portion of the mesopores contain micelles of supramolecular templates shaped to induce mesoporous ordering of hexagonal symmetry, and wherein the supramolecular templates possess one or more dimensions larger than dimensions of micropores of the crystalline microporous material to constrain diffusion into micropores of the crystalline microporous material, wherein the dimensions relate to a head group of a supramolecular template, a tail group of a supramolecular template, or a co-template arrangement that constrain diffusion into micropores of the crystalline microporous material, and wherein if the crystalline microporous material possesses micropores of various dimensions, the one or more dimensions of the supramolecular templates are larger than the largest micropores of the crystalline microporous material.

9. The composition of matter as in claim 8 , wherein said crystalline microporous material is a zeolite having FAU framework.

10. The composition of matter as in claim 9 , wherein the supramolecular template comprises dimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, derivatives of dimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, dimethylhexadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, derivatives of dimethylhexadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium iodide, or derivatives of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium iodide.

11. The composition of matter as in claim 8 , wherein said crystalline microporous material comprises a zeolite or zeolite-type material.

12. The composition of matter as in claim 8 , wherein said crystalline microporous material is a zeolite having a framework selected from the group consisting of AEI, *BEA, CHA, FAU, MFI, MOR, LTL, LTA and MWW.

13. The composition of matter as in claim 8 , wherein the supramolecular template contains at least one moiety, as a head group or a tail group, selected from the group consisting of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates and combinations comprising one of the foregoing moieties, wherein the moieties are characterized by one or more dimensions that are larger than dimensions of micropores of the crystalline microporous material to constrain diffusion into micropores of the crystalline microporous material.

14. The composition of matter as in claim 8 , wherein the supramolecular template comprises at least one of: aromatic quaternary ammonium compounds, branched alkyl chain quaternary ammonium compounds, alkyl benzene sulfonates, alkyl benzene phosphonates, alkyl benzene carboxylates, or substituted phosphonium cations; and (b1) and a constituent group comprising at least one of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates or phosphates, as a head group; or (b2) and a constituent group comprising at least one of organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates or phosphates, as a tail group, wherein the dimensions of the head group or the tail group are larger than dimensions of micropores of the crystalline microporous material to constrain diffusion into micropores of the crystalline microporous material.

15. The composition of matter as in claim 8 , wherein the supramolecular template comprises a quaternary ammonium compound and a constituent group comprising one or more bulky organosilane or alkoxysilyl substituents, wherein the dimensions of the constituent group is larger than dimensions of micropores of the crystalline microporous material to constrain diffusion into micropores of the crystalline microporous material.

16. The composition of matter as in claim 8 , wherein the supramolecular template comprises dimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, derivatives of dimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, dimethylhexadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, derivatives of dimethylhexadecyl[3-(trimethoxysilyl)propyl] ammonium chloride, [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium iodide, or derivatives of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium iodide.

17. A hydrocracking catalyst comprising the hierarchically ordered crystalline microporous material as in claim 5 , an inorganic oxide component as a binder, and an active metal component, wherein the hierarchically ordered crystalline microporous material comprises about 0.1-99 wt % of the hydrocracking catalyst.

18. The hydrocracking catalyst as in claim 17 , wherein the inorganic oxide component comprises alumina.

19. The hydrocracking catalyst as in claim 18 , wherein the crystalline microporous material comprises FAU zeolite.

20. The hydrocracking catalyst as in claim 19 , wherein the active metal component comprises oxides or sulfides of one or more of Mo, W, Co or Ni.

21. The hydrocracking catalyst as in claim 17 , wherein the inorganic oxide component is selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, silica-alumina-zirconia, alumina-zirconia-titania, phosphorous-alumina-zirconia, alumina-zirconia-titania and phosphorus-alumina-titani

Assignees

• Saudi Arabian Oil Co
• Univ King Abdullah Sci & Tech

Inventors

• Parsapur Rajesh Kumar
• Hodgkins Robert P
• Koseoglu Omer Refa
• Huang Kuo-Wei
• Sedjerari Anissa Bendjeriou

Classifications

• C10G47/20 Primary

  the catalyst containing other metals or compounds thereof · CPC title

• C01P2002/76

  by a space-group or by other symmetry indications · CPC title

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title