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US-12616965-B2 - Hierarchically ordered crystalline microporous materials with long-range mesoporous order having cubic symmetry

US12616965B2US 12616965 B2US12616965 B2US 12616965B2US-12616965-B2

Abstract

A composition of matter is provided comprising hierarchically ordered crystalline microporous material having well-defined long-range mesoporous ordering of cubic 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 cubic symmetry observable by microscopy.

Inventors

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

Assignees

  • SAUDI ARABIAN OIL COMPANY
  • KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY

Dates

Publication Date
20260505
Application Date
20250811

Claims (20)

  1. 1 . A composition of matter comprising hierarchically ordered crystalline microporous material having well-defined long-range mesoporous ordering of cubic 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 of cubic mesophase symmetry 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 is observable by microscopy including mesopore periodicity repeating over a length of greater than 50 nm.
  2. 2 . The composition of matter as in claim 1 , wherein the cubic mesophase possess Ia-3d, Fm-3m, Pm-3n, Pn-3m or Im-3m symmetry.
  3. 3 . The composition of matter as in claim 1 , wherein the cubic mesophase possess Ia-3d symmetry and secondary peaks in XRD are present at one or more of (220), (321), (400), (420) or (332) reflections.
  4. 4 . The composition of matter as in claim 1 , wherein the cubic mesophase possess Ia-3d symmetry and long-range ordering is observable by microscopy viewing an electron beam down a [311], [111] or [110] zone axis.
  5. 5 . The composition of matter as in claim 1 , wherein the cubic mesophase possess Fm-3m symmetry and long-range ordering is observable by microscopy viewing an electron beam down a [001] or [110] zone axis.
  6. 6 . The composition of matter as in claim 1 , wherein said crystalline microporous material comprises a zeolite, or a zeolite-type material selected from the group consisting of aluminophosphates, silicon-substituted aluminophosphates, metal-containing aluminophosphates and zeolitic siliceous only framework material.
  7. 7 . 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.
  8. 8 . The composition of matter as in claim 1 , wherein said parent crystalline microporous material is a zeolite having FAU framework.
  9. 9 . A hydrocracking catalyst comprising the hierarchically ordered crystalline microporous material as in claim 6 , an inorganic oxide component as a binder, and an active metal component comprising one or more metals selected from the Periodic Table of the Elements IUPAC Groups 6, 7, 8, 9 or 10.
  10. 10 . The hydrocracking catalyst as in claim 9 , wherein the hierarchically ordered crystalline microporous material comprises about 0.1-99 wt % of the hydrocracking catalyst.
  11. 11 . The hydrocracking catalyst as in claim 10 , 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-titania.
  12. 12 . The hydrocracking catalyst as in claim 10 , wherein the inorganic oxide component comprises alumina.
  13. 13 . The hydrocracking catalyst comprising the hierarchically ordered crystalline microporous material as in claim 9 , wherein the hierarchically ordered crystalline microporous material comprises about 20-50 wt % of the hydrocracking catalyst and the inorganic oxide component comprises alumina.
  14. 14 . The hydrocracking catalyst as in claim 13 , wherein the active metal component comprises one or more of Mo, W, Co or Ni (oxides or sulfides).
  15. 15 . A method for hydrocracking hydrocarbon oil, comprising: hydrocracking hydrocarbon oil with a hydrocracking catalyst as in claim 14 .
  16. 16 . The method as in claim 15 , wherein the hydrocarbon oil comprises a recycle stream obtained from hydrocracking of VGO, straight run VGO or pre-treated straight run VGO, with selectivity to naphtha and middle distillates tailored as a function of the cubic symmetry mesophase.
  17. 17 . A method for hydrocracking hydrocarbon oil, comprising: hydrocracking hydrocarbon oil with a hydrocracking catalyst as in claim 9 .
  18. 18 . The hydrocracking catalyst as in claim 9 , wherein the hierarchically ordered crystalline microporous material comprises about 20-50 wt % of the hydrocracking catalyst.
  19. 19 . The hydrocracking catalyst as in claim 18 , wherein the active metal component comprises one or more of Mo, W, Co or Ni (oxides or sulfides).
  20. 20 . A method for hydrocracking hydrocarbon oil, comprising: hydrocracking hydrocarbon oil with a hydrocracking catalyst as in claim 19 .

Description

RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 18/151,892 filed Jan. 9, 2023, which is a continuation-in-part of U.S. patent application Ser. No. 17/857,447 filed Jul. 5, 2022, now U.S. Pat. No. 12,152,204, the contents of which are incorporated herein by reference. FIELD OF THE DISCLOSURE The present disclosure relates to hierarchically ordered crystalline microporous materials. BACKGROUND OF THE DISCLOSURE Zeolites are microporous aluminosilicate materials possessing well-defined structures and uniform pore sizes that can be measured in nanometers or angstroms (∪) (pores typically up to about 20 Å). Typically, zeolites comprise framework atoms such as silicon, aluminum and oxygen arranged as silica and alumina tetrahedra. Zeolites are generally hydrated aluminum silicates that can be made or selected with a controlled porosity and other characteristics, and typically contain cations, water and/or other molecules located in the porous network. Hundreds of natural and synthetic zeolite framework types exist with a wide range of applications. Numerous zeolites occur naturally and are extensively mined, whereas a wealth of interdependent research has resulted in an abundance of synthetic zeolites of different structures and compositions. The unique properties of zeolites and the ability to tailor zeolites for specific applications has resulted in the extensive use of zeolites in industry as catalysts (e.g., catalytic cracking of hydrocarbons or as components in catalytic convertors), molecular sieves, adsorbents (e.g., drying agents), ion exchange materials (e.g., water softening) and for the separation of gases. Certain types of zeolites find application in various processes in petroleum refineries and many other applications. The zeolite pores can form sites for catalytic reactions, and can also form channels that are selective for the passage of certain compounds and/or isomers to the exclusion of others. Zeolites can also possess an acidity level that enhances its efficacy as a catalytic material or adsorbent, alone or with the addition of active components. Described below is only one of the hundreds of types of zeolites that are identified by the International Zeolite Association (IZA). Properties and uses of many of these are well known. Zeolite Y (also known as Na-Y zeolite or Y-type faujasite zeolite) is a well-known material for its zeolites have ion-exchange, catalytic and adsorptive properties. Zeolite Y is also a useful starting material for production of other zeolites such as ultra-stable y-type zeolite (USY). Like typical zeolites, faujasite is synthesized from alumina and silica sources, dissolved in a basic aqueous solution and crystallized. The faujasite zeolite has a framework designated as FAU by the IZA, and are formed by 12-ring structures having made of supercages with pore opening diameters of about 7.4 angstroms (Å) and sodalite cages with pore opening diameters of about 2.3 Å. Faujasite zeolites are characterized by a 3-dimensional pore structure with pores running perpendicular to each other in the x, y, and z planes. Secondary building units can be positioned at 4, 6, 6-2, 4-2, 1-4-4 or 6-6. An example silica-to-alumina ratio (SAR) range for faujasite zeolite is about 2 to about 6, typically with a unit cell size (units a, b and c) in the range of about 24.25 to 24.85 Å. Faujasite zeolites are typically considered X-type when the SAR is at about 2-3, and Y-type when the SAR is greater than about 3, for instance about 3-6. Typically, faujasite is in sodium form and can be ion exchanged with ammonium, and an ammonium form can be calcined to transform the zeolite to its proton form. Whereas zeolites have found great utility in their ability to select between small molecules and different cations, mesoporous solids (pores between about 20 and 500 Å) offer possibilities for applications for species up to an order of magnitude larger in dimensions such as nanoparticles and enzymes. The comparatively bulky nature of such species hinders diffusion through the microporous zeolite network, and thus, a larger porous system is required to effectively perform an analogous molecular sieving action for the larger species. Mesoporous silicas are amorphous; however, it is the pores that possess long-range order with a periodically aligned pore structure and uniform pore sizes on the mesoscale. Mesoporous silicas offer high surface areas and can be used as host materials to introduce additional functionality for a diverse range of applications such as adsorption, separation, catalysis, drug delivery and energy conversion and storage. An attractive property of ordered structures is that their architecture may be described in relation to their symmetry. The regular form of crystals is associated with the regular arrangements of the sub-units comprising the crystal, and hence, the symmetry of the crystal is connected to the symmetry of the sub-units. For ex