IP Library › Granted Patent US 12,290,799
Granted Patent B2
US 12,290,799 · App. 17/857,503 · Granted May 6, 2025

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

Inventors: Rajesh Kumar Parsapur (Thuwal, SA); Robert P. Hodgkins (Dhahran, SA); Omer Refa Koseoglu (Dhahran, SA); Kuo-Wei Huang (Thuwal, SA); Anissa Bendjeriou Sedjerari (Thuwal, SA)
Assignees: Saudi Arabian Oil Company; King Abdullah University of Science and Technology
B01J29/166B01J21/04C01B33/2853C01B33/2876C10G47/20C01P2002/72C01P2002/74C01P2002/76C01P2004/04
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Quick Facts
Patent No.
US 12,290,799
App. No.
17/857,503
Granted
May 6, 2025
Kind
B2
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.

Claims (23)

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-titania.

22. The hydrocracking catalyst as in claim 17 , wherein the active metal component comprises one or more metals selected from the Periodic Table of the Elements IUPAC Groups 6, 7, 8, 9 or 10.

23. A method for hydrocracking hydrocarbon oil, comprising: hydrocracking hydrocarbon oil with a hydrocracking catalyst as in claim 22 .

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 5, 2022
From: HODGKINS, ROBERT P.; KOSEOGLU, OMER REFA
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 060398/0952 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 5, 2022
From: PARSAPUR, RAJESH KUMAR; HUANG, KUO-WEI; SEDJERARI, ANISSA BENDJERIOU
To: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY
Reel/Frame 060399/0127 →
Continuity (1)
Related Publication 20240009657A1 · Jan 11, 2024
References Cited (57)
US 10118163B1 · Zhang · 2018 [cited by applicant]
US 20060096891A1 · Stamires et al. · 2006 [cited by applicant]
US 20130292300A1 · Ying · 2013 [cited by examiner]
US 20140286846A1 · Suib · 2014 [cited by examiner]
US 20160137516A1 · Kegnaes et al. · 2016 [cited by applicant]
US 20160167973A1 · Boorse et al. · 2016 [cited by applicant]
US 20170267537A1 · Machoke et al. · 2017 [cited by applicant]
US 20180194636A1 · Cheng et al. · 2018 [cited by applicant]
US 20180311652A1 · Zhang et al. · 2018 [cited by applicant]
US 20180345217A1 · Goffe · 2018 [cited by applicant]
US 20180345218A1 · Goffe · 2018 [cited by applicant]
US 20190039054A1 · Pilyugina · 2019 [cited by applicant]
US 20190232261A1 · Yanson et al. · 2019 [cited by applicant]
US 20200139355A1 · Cheon et al. · 2020 [cited by applicant]
US 20200165140A1 · Verboekend et al. · 2020 [cited by applicant]
US 20200223708A1 · Bauer et al. · 2020 [cited by applicant]
US 20200398252A1 · Ma et al. · 2020 [cited by applicant]
US 20210047193A1 · Choi et al. · 2021 [cited by applicant]
US 20210179437A1 · Cheon et al. · 2021 [cited by applicant]
US 20210347647A1 · Lim et al. · 2021 [cited by applicant]
US 20220032275A1 · Zhang · 2022 [cited by applicant]
CN 105692644A · 2016 [cited by applicant]
WO 2019010700A1 · 2019 [cited by applicant]
WO 2020036985A1 · 2020 [cited by applicant]
WO 2021126298A1 · 2021 [cited by applicant]
Wong et al. “Surfactant-templated Mesostructured Materials: Synthesis and Compositional Control”, Jan. 1, 2004 (Jan. 1, 2004), Nanoporous Materials—Science and Engineering, Imperial College Press, London (GB), pp. 125-1… [cited by examiner]
Beck et al. “A new family of mesoporous molecular sieves prepared with liquid crystal templates.” Journal of the American Chemical Society 114.27 (1992): 10834-10843. [cited by applicant]
Choi et al. “Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity.” Nature Materials 5.9 (2006): 718-723. [cited by applicant]
Garcia-Martinez et al. “Mesostructured zeolite Y—high hydrothermal stability and superior FCC catalytic performance.” Catalysis Science & Technology 2.5 (2012): 987-994. [cited by applicant]
Nayat et al. “Assemblies of mesoporous FAU-type zeolite nanosheets.” Angewandte Chemie International Edition 51.8 (2012): 1962-1965. [cited by applicant]
Jia et al. “Modern synthesis strategies for hierarchical zeolites: Bottom-up versus top-down strategies.” Advanced Powder Technology 30.3 (2019): 467-484. [cited by applicant]
Kang et al. “Hofmeister series: Insights of ion specificity from amphiphilic assembly and interface property.” ACS Omega 5.12 (2020): 6229-6239. [cited by applicant]
Kerstens et al. “State of the art and perspectives of hierarchical zeolites: practical overview of synthesis methods and use in catalysis.” Advanced Materials 32.44 (2020): Wiley Online Library. 2004690. [cited by applicant]
Kresge et al. “Ordered mesoporous molecular sieves synthesized by a liquid crystal template mechanism.” Nature 359.6397 (1992): 710-712. [cited by applicant]
Mendoza-Castro et al. “Surfactant-Templated Zeolites: From Thermodynamics to Direct Observation.” Advanced Materials Interfaces 8.4 (2021): 2001388. [cited by applicant]
Moller et al. “Pores within pores—how to craft ordered hierarchical zeolites.” Science 333.6040 (2011): 297-298. [cited by applicant]
Na et al. “Directing zeolite structures into hierarchically nanoporous architectures.” Science 333.6040 (2011): 328-332. [cited by applicant]
Raman et al. “Template-based approaches to the preparation of amorphous, nanoporous silicas.” Chemistry of Materials 8.8 (1996): 1682-1701. [cited by applicant]
Roth et al. “Two-dimensional zeolites: current status and perspectives.” Chemical Reviews 114.9 (2014): 4807-4837. [cited by applicant]
Verboekend et al. “Hierarchical zeolites by desilication: Occurrence and catalytic impact of recrystallization and restructuring.” Crystal Growth & Design 13.11 (2013): 5025-5035. [cited by applicant]
Schwieger et al. “Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity.” Chemical Society Reviews 45.12 (2016): 3353-3376. [cited by applicant]
Zana (Ed.) “Chapter 1: Introduction to Surfactants and Surfactant Self-Assemblies.” Dynamics of surfactant self-assemblies: micelles, microemulsions, vesicles and lyotropic phases. CRC Press, Taylor & Francis Group. Boc… [cited by applicant]
Zhao et al. “Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures.” Journal of the American Chemical Society 120.24 (199… [cited by applicant]
Zhu et al. “Synthesis of hierarchical zeolites using an inexpensive mono-quaternary ammonium surfactant as mesoporogen.” Chemical communications 50.93 (2014): 14658-14661. [cited by applicant]
Mei et al. “Hierarchically porous Beta/SBA-16 with different silica-alumina ratios and the hydrodesulfurization performances of DBT and 4, 6-DMDBT.” Petroleum Science 19.1 (2022): 375-386. [cited by applicant]
Wang et al. “Hierarchical ZSM-5 zeolite with radial mesopores: preparation, formation mechanism and application for benzene alkylation.” Frontiers of Chemical Science and Engineering 14 (2020): 248-257. [cited by applicant]
Zhang et al. “Synthesis, characterization, and catalytic performance of NiMo catalysts supported on hierarchically porous Beta-KIT-6 material in the hydrodesulfurization of dibenzothiophene.” Journal of Catalysis 274.2 … [cited by applicant]
International Search Report and Written Opinion of PCT Application No. PCT/US2023/069238, mailed Oct. 24, 2023. [cited by applicant]
Beck et al,; Molecular or Supramolecular Templating: Defining the Role of Surfactant Chemistry in the Formation of Microporous and Mesoporous Molecular Sieves; Chemistry of Materials, col. 6, No. 10, Oct. 1, 1994; pp. 1… [cited by applicant]
Wong et al; Surfactant-templated Mesostructured Materials: Synthesis and Compositional Control; Nanoporous Materials—Science and Engineeting, Imperial College Press, London, Jan. 1, 2004; pp. 125-164. [cited by applicant]
Parsapur et al.; Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Framworks for Vacuum Gas Oil Hydrockracking; Angew. Chem. Int. Ed. 2024, 63, e202314217; 10 pages. [cited by applicant]
Liu et al.; Y/MCM-41 composites assembled from nanocrystals; Elsevier; Microporous and Mesoporous Materials 181; (2013) 116-122. [cited by applicant]
Non Final Office Action in corresponding U.S. Appl. No. 17/857,572, mailed Dec. 27, 2023; 26 pages. 2023. [cited by applicant]
Response to Non-Final Office Action in corresponding U.S. Appl. No. 17/057,572, filed Mar. 25, 2024; 46 pages. 2024. [cited by applicant]
Final Office Action in corresponding U.S. Appl. No. 17/857,572, mailed Jun. 17, 2024; 25 pages. 2024. [cited by applicant]
Response to Final Office Action in corresponding U.S. Appl. No. 17/857,572, filed Oct. 30, 2024; 33 pages. 2024. [cited by applicant]
International Preliminary Report on Patentability for corresponding PCT Application No. PCT/US2023/069238 dated Dec. 18, 2024 (8 pages). [cited by applicant]