Hierarchical ordered crystalline microporous material with long-range mesoporosity having hexagonal symmetry

Abstract

A composition is provided that includes a hierarchical ordered crystalline microporous material having a hexagonal symmetric defined long-range mesoporous order. The composition possesses mesopores having walls of the crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material. The long-range order is defined by the presence of secondary peaks in an X-ray diffraction (XRD) pattern and / or by hexagonal symmetry observable by microscopy.

Description

Technical Field

[0001] The present disclosure relates to hierarchical ordered crystalline microporous materials.

Background Art

[0002] Zeolites are microporous aluminosilicate materials that possess a defined structure and uniform pore diameters that can be measured in nanometers or angstroms (Å) (the pores are typically up to about 20 Å maximum). Typically, zeolites contain framework atoms such as silicon, aluminum, and oxygen arranged as silica and alumina tetrahedra. Zeolites are generally hydrated aluminosilicates that can be made or selected based on controlled porosity and other properties, and typically contain cations, water, and / or other molecules located within the porous network. Hundreds of natural and synthetic zeolite framework types exist for a wide range of applications. Many zeolites occur naturally and are mined extensively, and a large amount of interdependent research has led to synthetic zeolites with a wide variety of structures and compositions. The unique properties of zeolites and the ability to tailor them for specific applications have led to the widespread use of zeolites in industry as catalysts (e.g., for catalytic cracking of hydrocarbons or as components in catalytic converters), molecular sieves, adsorbents (e.g., desiccants), ion exchange materials (e.g., water softeners), and for gas separation. Certain types of zeolites have found use in various processes in petroleum refining units and in many other applications. The pores of zeolites can form sites for catalytic reactions and can also form selective channels for the passage of certain compounds and / or isomers over others. Zeolites can also possess acidity levels that enhance their effectiveness as catalyst materials or adsorbents, either alone or by addition of active components. Only one of the hundreds of types of zeolites clarified by the International Zeolite Association (IZA) is described below. Many of these properties and uses are well known.

[0003] Zeolite Y (also known as Na-Y zeolite or faujasite Y zeolite) is a well-known material whose zeolite has ion exchange, catalytic, and adsorption properties. Zeolite Y is also a useful starting material for producing other zeolites such as ultrastable Y zeolite (USY). Like typical zeolites, faujasite is synthesized from alumina and silica sources, dissolved in a basic aqueous solution, and crystallized. Faujasite zeolite has a framework designated as FAU by the IZA and is formed by a 12-ring structure made up of supercages with a pore opening diameter of about 7.4 angstroms (Å) and sodalite cages with a pore opening diameter of about 2.3 Å. Faujasite zeolite is characterized by a three-dimensional pore structure with pores running perpendicular to each other in the x, y, and z planes. The secondary building units can be positioned at 4, 6, 6-2, 4-2, 1-4-4, or 6-6. The exemplary range of the silica-to-alumina ratio (SAR) for faujasite zeolite is from about 2 to about 6, and typically has unit cells (unit a, b, and c) in the range of about 24.5 to 24.85 Å. Faujasite zeolite is typically regarded as X-type when the SAR is about 2-3 and Y-type when the SAR is greater than about 3, for example, when it is about 3-6. Typically, faujasite is in the sodium form and can be ion-exchanged with ammonium, and the ammonium form can be calcined to convert the zeolite to its proton form.

[0004] While zeolites have found great utility in their ability to select between small molecules and various cations, mesoporous solids (pores between about 20 and 500 Å) offer potential for applications involving chemical species that are up to an order of magnitude larger in size, such as nanoparticles and enzymes. The relatively bulky nature of such chemical species hinders diffusion through the microporous zeolite network, and thus, a larger porous system is required to effectively perform a similar molecular sieving action for larger chemical species.

[0005] Mesoporous silica is amorphous; however, it has pores with a periodically arranged pore structure and long-range order with a uniform pore diameter at the mesoscale. Mesoporous silica provides a high surface area and can be used as a host material to introduce additional functionality for a variety of applications such as adsorption, separation, catalysis, drug delivery, and energy conversion and storage.

[0006] An attractive property of ordered structures is that their architecture can be described in terms of their symmetry. A defined crystal shape is associated with a defined arrangement of sub-units that make up the crystal, and thus the symmetry of the crystal is related to the symmetry of the sub-units. For example, seven clearly different three-dimensional crystal units are presented in Table 1. Crystal systems can be subdivided on the basis of the symmetry elements present, which are collectively called point groups and are presented in Table 2. For example, 3m implies the presence of a mirror plane with a three-fold axis of rotation. In the 3 / m (or 6) class, the mirror plane is perpendicular to the three-fold axis of rotation. In two-dimensional spaces such as lamellar systems with fewer dimensions than 3D, there are four crystal systems: hexagonal, tetragonal, orthorhombic, and monoclinic.

[0007] The defined microporous structure of zeolites provides a blend of important physicochemical functionalities highly desirable in various industrial practices. Their molecular-sized pore channels, embedded with adjustable acid / base sites, can geometrically discriminate the entry of guest species and govern shape-selective transformations. Such remarkable properties uniquely exhibited by zeolites demonstrate unprecedented importance in numerous chemical technologies, including but not limited to petroleum refining, detergents, and wastewater reduction, which deeply impact the world economy and environment. However, the performance of zeolites is often hampered as a result of their insufficient mass transfer induced by configurational diffusion within narrow micropores. Therefore, alleviating the essential mass transfer limitations is crucial to exploring the maximum potential of zeolites in diverse energy economies and thereby enhancing the accessibility to internal functional sites. Another drawback of microporous zeolites as catalysts in certain reactions is their susceptibility to coking, which can lead to accelerated catalyst deactivation and product selectivity.

[0008] In this regard, hierarchically ordered zeolites (HOZs) possessing an ordered mesoporous structure and zeolite mesopore walls are of great technological importance due to their exceptional properties. HOZs contain various layers of porosity, namely, mesopores and micropores. Hierarchically ordered zeolites offer advantages over traditional microporous zeolites, for example, by improving the diffusion of guest species to active sites, overcoming steric limitations, improving product selectivity, reducing coke formation, improving hydrothermal stability, and improving the accessibility of Brønsted acid sites and Lewis acid sites; simultaneously, they provide improved catalyst performance.

[0009] Numerous synthetic strategies for generating hierarchical zeolites are known and fall into two general categories: bottom-up approaches that involve the use of hard templates and soft templates, and top-down approaches that typically involve post-synthetic processing. Bottom-up strategies generally involve template formation techniques that are used in situ during zeolite crystallization, for example using a hard template (carbon source) or a soft template (surfactant). Top-down strategies generally involve post-synthetic modification of already formed zeolite crystals, for example by steam formation, dealumination (using an acid), or desilication (using a base). A weakness of known processes for generating hierarchically ordered zeolites is that the long-range ordering of the mesophase in the resulting zeolites is limited or absent, and the mesopores can be random in size, location, and ordering.

[0010] Base-mediated dealumination provides a direct route to creating mesoporosity in high-silica frameworks obtained from steam formation (see, e.g., Verboekend, D., Milina, M., Mitchell, S. & Perez-Ramirez, J. Hierarchical Zeolites by Desilication: Occurrence and Catalytic Impact of Recrystallization and Restructuring. Crys. Growth Des. 13, 5025~(2013)). In particular, integrating organic templates during the dealumination process significantly improves crystallinity and mesoporosity (see, e.g., Garcia-Martinez, J., Johnson, M., Valla, J., Li, K. & Ying, J. Y. Mesostructured Zeolite Y - High Hydrothermal Stability and Superior FCC Catalytic Performance. Catal. Sci. Tech. 2, 987 (2012); Mendoza-Castro, M. J., Serrano, E., Linares, N. & Garcia-Martinez, J. Surfactant-Templated Zeolites: From Thermodynamics to Direct Observation. Adv. Mater. Interfaces 8, 2001388 (2020)). However, such post-synthesis modification strategies typically lack control over dissociation and self-organization processes, leading to insufficiently interconnected mesopores (see, e.g., Schwieger, W. et al., Hierarchy Concepts: Classification and Preparation Strategies for Zeolite Containing Materials with Hierarchical Porosity. Chem. Soc. Rev. 45, 3353~3376, doi:10.1039 / c5cs00599j (2016)).

Prior Art Documents

Patent Document

[0011]

Patent Document 1

Patent Document 2

Non-Patent Document

[0012]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

[0013] In view of the conventional attempts to generate hierarchically ordered zeolites, hierarchically ordered zeolites are still in demand in the art. Regarding these and other problems in the art, the present disclosure aims to provide a technical solution regarding a composition of hierarchically ordered zeolites having a defined long-range mesoporous ordering with hexagonal symmetry. [Means for Solving the Problems]

[0014] A composition is provided that includes a crystalline microporous material such as a hierarchically ordered zeolite or zeolite-type material. These hierarchically ordered crystalline mesoporous materials have a hexagonal symmetric defined long-range mesoporous order that includes a group of mesostructures between the mesopores having the walls of the crystalline microporous material and the mesopores composed of the crystalline microporous material. The long-range order is defined by the presence of secondary peaks in the X-ray diffraction (XRD) pattern and / or the hexagonal symmetry observable by microscopy.

[0015] In certain embodiments, the composition includes a hierarchically ordered crystalline microporous material having a hexagonal symmetric defined long-range mesoporous order that includes a group of mesostructures between the mesopores having the walls composed of the crystalline microporous material and the mesopores of the crystalline microporous material. At least a portion of the mesopores contain micelles of a supramolecular template shaped to induce a hexagonal symmetric mesoporous order. The supramolecular template has one or more dimensions larger than the dimensions of the micropores of the crystalline microporous material so as to limit diffusion into the micropores of the crystalline microporous material, and this dimension is related to the head group of the supramolecular template, the tail group of the supramolecular template, or a cotemplate arrangement configuration that limits diffusion into the micropores of the crystalline microporous material. In certain embodiments, an ionic cosolute is present in the hierarchically ordered crystalline microporous material; in certain embodiments, the ionic cosolute includes SO4 -2 . In certain embodiments, the supramolecular template is characterized by a surfactant packing parameter g in the range of about 0.4 to 0.6, where g = V / a0l, where V = the total volume of the surfactant tail of the supramolecular template, a0 = the area of the head group of the supramolecular template, and l = the length of the surfactant tail of the supramolecular template. In certain embodiments, the molar ratio of the supramolecular template to the cosolute is in the range of about 0.8 to 1.3.

[0016] In certain embodiments, the hexagonal mesophase has p6m, p6mm, or P63 / mmc symmetry. In certain embodiments, the hexagonal mesophase has p6mm symmetry and the secondary peaks in XRD are present in the (11) and / or (20) reflections. In certain embodiments, the hexagonal mesophase has p6mm symmetry and the long-range order is observable by microscopy looking at an electron beam perpendicular to the mesopores along the

[0110] zone axis or parallel to the mesopores along the

[0001] zone axis. In certain embodiments,

[0017] In certain embodiments, the parent crystalline microporous material comprises a zeolite or zeolite-type material. For example, the parent 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. In certain embodiments, the parent crystalline microporous material is a zeolite having a FAU framework.

[0018] In certain embodiments, there is provided a hydrocracking catalyst comprising a hierarchical ordered zeolite described herein, an inorganic oxide as a binder, and an active metal component. For example, the hierarchical ordered crystalline microporous material comprises the hydrocracking catalyst in an amount of about 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40 mass%. The inorganic oxide component is selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, aluminaboria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, silica-alumina-zirconia, alumina-zirconia-titania, phosphorus-alumina-zirconia, alumina-zirconia-titania, and phosphorus-alumina-titania. In certain embodiments, the inorganic oxide component comprises alumina. In certain embodiments, the zeolite comprises a FAU zeolite. In certain embodiments, the active metal component comprises one or more of Mo, W, Co, or Ni (oxide or sulfide). The active metal component comprises one or more metals selected from Groups 6, 7, 8, 9, or 10 of the IUPAC Periodic Table of the Elements.

[0019] In certain embodiments, there is provided a method for hydrocracking a hydrocarbon oil, comprising the step of hydrocracking a hydrocarbon oil with a hydrocracking catalyst comprising a hierarchical ordered zeolite described herein. In certain embodiments, the hydrocarbon oil comprises a recycle stream obtained from hydrocracking of VGO, straight-run VGO, or pretreated straight-run VGO, based on the selectivity to naphtha adjusted as a function of the hexagonal symmetric mesophase.

[0020] Any combination of the various embodiments and examples disclosed herein can be used. These and other aspects and features can be understood from the following description of certain embodiments, the accompanying drawings, and the claims.

[0021] The method of the present disclosure will be described in further detail below with reference to the accompanying drawings in which the same reference numerals are used for the same or similar elements.

Brief Description of the Drawings

[0022]

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Mode for Carrying Out the Invention

[0023] Compositions are provided that include hierarchically ordered crystalline microporous materials (“CMMs”). These hierarchically ordered crystalline microporous materials (“HOCMMs”) have a hexagonal symmetric defined long-range mesoporous order that includes mesopores having a group of mesostructures between the walls of the crystalline microporous material and the mesopores of the CMM. The long-range ordering is defined by the presence of secondary peaks in the X-ray diffraction (XRD) pattern and / or hexagonal symmetry observable by microscopy. In certain embodiments, for example, prior to calcination of the synthesized HOCMM, at least a portion of the mesopores contain micelles of a supramolecular template that is shaped to induce a hexagonal symmetric mesoporous order, and this supramolecular template has one or more dimensions larger than the dimensions of the micropores of the crystalline microporous material so as to limit diffusion into the micropores of the crystalline microporous material. The dimensions relate to the head group of the supramolecular template, the tail group of the supramolecular template, or the co-template arrangement configuration that limits diffusion into the micropores of the CMM. The HOCMMs are synthesized by using base-mediated reassembly, by decomposition of the parent CMM to the level of structural building units that are oligomers of the parent CMM, and by minimizing or avoiding amorphization / structural collapse. The CMM decomposition and self-assembly are comprehensively controlled to produce HOCMMs by the methods herein that have a hexagonal symmetric mesoporous order, including embodiments using ionic cosolutes. Methods for obtaining the compositions, including those disclosed herein, are disclosed in U.S. Patent Application No. 17 / 857,671, filed July 5, 2022, and U.S. Patent Application No. 18 / 151,782, filed January 9, 2023, both of which are commonly assigned and have the title “Methods for Synthesis of Hierarchically Ordered Crystalline Microporous Materials with Long-Range Mesoporous Order” and are hereby incorporated herein by reference in their entirety.

[0024] In certain embodiments of the reassembly for generating the compositions of the present specification: the rate and extent of CMM degradation are controlled by using urea as a base in situ and by mediating the hot water temperature to control the hydrolysis of urea and finely tune the pH of the solution; the extent of degradation to smaller oligomers is controlled by surfactant-CMM interactions during the initial stages of degradation, whereby the influence of ion-specific interactions, i.e., the anionic Hofmeister effect (AHE) on supramolecular self-assembly, dictates the formation of a hierarchical ordered structure with hexagonal mesopore symmetry; in certain embodiments, the hierarchical ordered structure possesses hexagonal P6mm mesopore symmetry.

[0025] According to an embodiment of the method for generating the composition of the present specification, the parent CMM is formed in an aqueous suspension by an alkaline reagent and a supramolecular templating agent. In an additional embodiment, the aqueous suspension contains an ionic co-solute as an additional anion separated from the anion that pairs with the cation of the supramolecular template. The system is maintained under conditions that induce cleavage of the parent CMM into oligomeric units of the CMM having very few monomer units and hierarchical reassembly of the oligomeric units into a mesostructure. The conditions of the system (including the temperature and time of crystallization), the choice and concentration of the supramolecular template, and the choice and concentration of the alkaline reagent are adjusted to control the cleavage of the parent CMM into oligomeric units and the reassembly of those oligomeric units around the shape of the supramolecular template micelle. The degradation of the parent CMM is promoted to the extent of oligomer formation while minimizing monomer formation, which is controlled by the choice of supramolecular template, alkaline reagent, ionic co-solute if necessary, and hydrothermal conditions (including temperature and time). In certain embodiments, a substantial, significant, or majority portion of the parent CMM is cleaved into oligomeric units, and any remainder thereof takes the form of monomeric units or atomic constituents of the CMM. In certain embodiments, the dimensions of the oligomeric units approximately correspond to the synthesized mesoporous structure and the wall thickness of the HOCMM. In certain embodiments, the interfacial curvature of the micelles and oligomeric units under reassembly is adjusted to the desired mesostructure and mesoporosity with the aid of an ionic co-solute and the Hofmeister effect if necessary.

[0026] Under effective crystallization conditions and times, and using an effective type of supramolecular template and an alkali reagent at effective relative concentrations, hierarchical ordering by the ensemble occurs after synthesis: the parent CMM is cleaved into oligomeric CMM units that are repositioned around the shaped micelles formed by the supramolecular template. Hierarchically ordered CMMs with defined long-range mesoporous order are formed by a supramolecular templating method using surfactant micelles. The mesoporous walls are characterized by the parent CMM. Effective supramolecular templates include those having one or more properties that form dimensions that block all, a substantial portion, a significant portion, or a majority of the supramolecular template molecules from entering the pores, channels, and / or cavities of the parent CMM. These methods disclosed herein cause base-mediated cleavage of CMM crystals into oligomeric components in the presence of a supramolecular template of the type / character disclosed herein, followed by reorganization around defined micelles by supramolecular templating to form a hierarchically ordered structure with a defined long-range mesoporous order of 2D-hexagonal symmetry.

[0027] The curvature or shape of the micelles results in a final 2D - hexagonal mesophase symmetry. The formation of micelles from supramolecular template molecules depends on factors such as the type of supramolecular template, the concentration of the supramolecular template, the presence or absence of ionic co - solutes, the type of CMM, the crystallization temperature, the type of alkaline reagent, the concentration of the alkaline reagent, the pH level of the system, and / or the presence or absence of other reagents. Generally, at low concentrations, the supramolecular template exists as individual entities. At higher concentrations, i.e., above the critical micelle concentration (CMC), micelles are formed. Hydrophobic interactions in a system containing a supramolecular template can change the packing shape of the supramolecular template into, for example, spherical, prolate, or cylindrical micelles, and then form a thermodynamically stable two - dimensional or three - dimensional liquid - crystalline phase of an ordered mesostructure (see, for example, Figure 1.4 in Zana, R. (ed.) (2005), Dynamics of Surfactant Self - Assemblies: Micelles, Microemulsions, Vesicles and Lyotropic Phases (1st ed.). CRC Press, Chapter 1, showing surfactant - based self - organization and surfactant packing parameters).

[0028] In certain embodiments, the Hofmeister series (HS), ion-specific effects, or lyotropic series are followed for the selection of supramolecular templates and / or ionic cosolutes that control the curvature or shape of the micelles (e.g., spheres, ellipsoids, cylinders, or single lamellar structures) (see, e.g., Beibei Kang, Huicheng Tang, Zengdian Zhao, and Shasha Song. “Hofmeister Series: Insights of Ion Specificity from Amphiphilic Assembly and Interface Property” ACS Omega 5 (2020): 6229–6239). In embodiments of the methods for synthesizing hierarchically ordered microporous crystalline materials having defined long-range mesoporous order disclosed herein, the mesophase transition of the hierarchical ensemble results in distinct mesostructures based on the anionic Hofmeister effect and supramolecular self-assembly. Anions of various sizes and charges carry various polarizabilities, charge densities, and hydration energies in aqueous solutions. When paired with the positive supramolecular template headgroups, these properties can affect the short-range electrostatic repulsion within the headgroups and the hydration at the micelle interface, and thus change the headgroup area (a0). Such ion-specific interactions can be the driving force in the change of micelle curvature and the induction of mesophase transition. HS (SO4 2- > HPO4 2- > OAc - > Cl - > Br - > NO3 - > ClO4 - > SCN -Based on (0), strongly hydrated ions (left side of HS) can increase the micelle curvature, while weakly hydrated ions can decrease the micelle curvature. The surfactant packing parameter, g = V / a0l (V = total volume of the surfactant tail, a0 = area of the head group, l = length of the surfactant tail), can be used to describe these mesophase transitions. In the embodiments of this specification, a hierarchical ordered structure having a defined long-range mesoporous order of 2D-hexagonal symmetry is formed by selecting a supramolecular template and an ionic cosolute.

[0029] In the method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order disclosed herein, the appropriate alkaline reagent comprises one or more basic compounds to maintain the system at a pH level greater than about 8. In certain embodiments, the alkaline reagent is provided at a concentration in an aqueous suspension of about 0.1 - 2.0 M. In certain embodiments, the alkaline reagent is provided at a concentration in an aqueous suspension of about 0.1 - 5 wt%. In certain embodiments, the alkaline reagent comprises urea. In certain embodiments, the alkaline reagent comprises ammonia. In certain embodiments, the alkaline reagent comprises ammonium hydroxide. In certain embodiments, the alkaline reagent comprises sodium hydroxide. In certain embodiments, the alkaline reagent comprises an alkali metal hydroxide comprising a hydroxide of sodium, lithium, potassium, rubidium, or cesium.

[0030] In certain embodiments, the alkali reagent is effective to enable controlled hydrolysis; for example, urea can be used as an alkali agent and during hydrolysis, urea reacts to form ammonium hydroxide. For example, a higher urea concentration can be used in an initial step and the basicity can be maintained by stepwise hydrolysis of urea. In such embodiments, the pH increases relatively slowly to a maximum pH as a function of time rather than by adding some amount of another alkali reagent such as ammonium hydroxide to the initial solution towards the maximum pH, which is beneficial for the process. Unlike conventional bases that act quickly, urea has a neutral pH under ambient conditions and can be uniformly dispersed throughout the zeolite micropores without affecting them.

[0031] In certain embodiments, the alkali reagent contains an alkylammonium cation having the general formula R X H 4-X N + [A - , where X = 1 - 4, R1, R2, R3, and R4 are the same or various C1 - C30 alkyl groups, and [A - is an anionic counterion that can be OH - , Br - , Cl - , or I - . In certain embodiments, the alkali reagent contains a quaternary ammonium cation having an alkoxysilyl group, a phosphonium group, an alkyl group, an alkyl group with a bulkier substituent, or an alkoxyl group with a bulkier substituent. In certain embodiments, the alkylammonium cation used in this regard functions as a base rather than a surfactant or template.

[0032] In certain embodiments using ammonia, ammonium hydroxide, or an alkali metal hydroxide, an amorphous material is also present in the product along with the crystalline material. In certain embodiments, calcining the as-made HOCMM reduces the amount of the apparent amorphous material present (e.g., a broad band overall at 25° (2θ) in XRD), which indicates an apparent “self-healing” after calcination. In certain embodiments, when directly compared to an alternative route such as NaOH or ammonium hydroxide, controlled hydrolysis from urea to ammonium hydroxide reduces the amount of the apparent amorphous material present in the HOCMM (e.g., a broad band overall at 25° (2θ) in XRD).

[0033] In a method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order as disclosed herein, a suitable surfactant as a supramolecular template is provided to assist in the reassembly and recrystallization of the decomposition components (oligomers) by shared and / or electronic valence interactions. The supramolecular template is provided at a concentration in an aqueous suspension of about 0.01 - 0.5 M. In certain embodiments, a suitable supramolecular template is provided at a concentration in an aqueous suspension of about 0.5 - 10 wt%. A suitable supramolecular template is characterized by restricted diffusion in the micropore channels of the parent CMM, called bulk surfactant or bulk supramolecular template. The diffusion of the supramolecular template molecules into the micropore-channels or cavities promotes CMM decomposition. This is minimized in the top-down method for synthesizing a hierarchical ordered CMM having a defined long-range mesoporous order as disclosed herein, and its effective supramolecular template minimizes the diffusion or partial diffusion into the CMM pore-channels, cavities, or window openings. Such a supramolecular template has dimensions suitable for blocking such diffusion. Suitable dimensions can be based on the dimensions of the head group and / or tail group of the supramolecular template. In certain embodiments, suitable dimensions can be based on a co-template having one or more components with stable head and / or tail groups, or can be a template system arranged and configured in such a way as to minimize or block the diffusion into the CMM pore-channels, cavities, or window openings. By minimizing the diffusion of the template into the CMM pore channels, CMM decomposition into oligomers, as well as the comprehensive reorganization and assembly into a hierarchical ordered CMM having a defined long-range mesoporous order as disclosed herein, is promoted. In certain embodiments, the supramolecular template is such that at least a substantial, significant, or major portion of the surfactant does not enter into the pores and / or channels of the CMM. For example, organosilane (about 0.7 nm) is relatively large compared to a quaternary ammonium surfactant having no such bulk group including cetyltrimethylammonium bromide (CTAB) (about 0.25 nm).In certain embodiments, the supramolecular template contains a long-chain linear group (> about 0.6 nm). In certain embodiments, the supramolecular template contains an aromatic or aromatic derivative group (> about 0.6 nm). In certain embodiments, the supramolecular template contains one or more bulk-like groups having dimensions based on modeling the molecular dimensions as a rectangular parallelepiped having dimensions A, B, and C using the van der Waals radius for each individual atom, and one or more, two or more, or all three of the dimensions A, B, and C are of a size sufficiently close or large enough to restrict diffusion into the micropores of the selected parent CMM.

[0034] In certain embodiments, surfactants effective as supramolecular templates contain 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 containing one of the foregoing moieties. In certain embodiments, an effective supramolecular template is an organosilane containing at least one hydroxysilyl as a head group moiety. In certain embodiments, an effective supramolecular template is an organosilane containing at least one hydroxysilyl as a tail group moiety. In certain embodiments, an effective supramolecular template is an organosilane containing at least one alkoxysilyl as a head group moiety. In certain embodiments, an effective supramolecular template is an organosilane containing at least one alkoxysilyl as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one aromatic as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one aromatic as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one branched alkyl as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one branched alkyl as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one sulfonate as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one sulfonate as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one carboxylate as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one carboxylate as a tail group moiety. In certain embodiments, an effective supramolecular template contains at least one phosphate as a head group moiety. In certain embodiments, an effective supramolecular template contains at least one phosphate as a tail group moiety. These moieties are characterized by one or more dimensions that limit diffusion into the pores of the parent CMM.In certain embodiments, where the CMM is characterized by pores of various dimensions, the selected moiety is characterized by one or more dimensions that limit diffusion into the largest pores of the parent CMM.

[0035] In certain embodiments, an effective supramolecular template contains at least one cationic moiety. In certain embodiments, an effective supramolecular template contains at least one cationic moiety selected from the group consisting of quaternary ammonium moieties and phosphonium moieties. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group having a terminal alkyl group with 6 to 24 carbon atoms. In certain embodiments, an effective supramolecular template contains two quaternary ammonium groups, and the alkyl group bridging the quaternary ammonium groups contains 1 to 10 carbon atoms. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group and at least one constituent moiety, the head group moiety described above. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group and at least one constituent moiety, the tail group moiety described above. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group, at least one constituent moiety, the head group moiety described above, and an alkyl group containing 1 to 10 carbon atoms that bridges at least one of the at least one quaternary ammonium group and at least one of the head groups. In certain embodiments, an effective supramolecular template contains at least one quaternary ammonium group, at least one constituent moiety, the tail moiety described above, and an alkyl group containing 1 to 10 carbon atoms that bridges at least one of the at least one quaternary ammonium group and at least one of the tail groups.

[0036] In certain embodiments, an effective supramolecular template comprises a quaternary ammonium compound and a structural group comprising one or more bulky organic silanes or alkoxysilyl substituents. In certain embodiments, an effective supramolecular template comprises a quaternary ammonium compound and a structural group comprising one or more long-chain organic silanes or alkoxysilyl substituents. In certain embodiments, an effective supramolecular template cation comprises dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium, or a derivative of dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium. In certain embodiments, an effective supramolecular template cation comprises dimethylhexadecyl(3-trimethoxysilyl-propyl)-ammonium, or a derivative of dimethylhexadecyl(3-trimethoxysilyl-propyl)-ammonium. In certain embodiments, an effective supramolecular template cation comprises a double-acyl-oxy amphiphilic organic silane, such as [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium, or a derivative of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilyl)propyl)-dimethylammonium.

[0037] In certain embodiments, an effective supramolecular template comprises a quaternary phosphonium compound and a structural group comprising one or more bulky aromatic substituents. In certain embodiments, an effective supramolecular template comprises a quaternary phosphonium compound and a structural group comprising one or more bulky alkoxysilyl or organic silane substituents.

[0038] In certain embodiments, an effective supramolecular template contains a tail group portion selected from the group consisting of an aromatic group having 6 to 50, 6 to 25, 10 to 50, or 10 to 25 carbon atoms, an alkyl group having 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, an aryl group having 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, or a combination of aromatic and alkyl groups having up to 50 carbon atoms. In certain embodiments, an effective supramolecular template contains a head group portion selected from the group consisting of an aromatic group having 6 to 50, 6 to 25, 10 to 50, or 10 to 25 carbon atoms, an alkyl group having 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, an aryl group having 1 to 50, 1 to 25, 5 to 50, 5 to 25, 10 to 50, or 10 to 25 carbon atoms, or a combination of aromatic and alkyl groups having up to 50 carbon atoms. In certain embodiments, an effective supramolecular template contains a co-templating agent selected from the group consisting of quaternary ammonium compounds (e.g., including quaternary alkylammonium cation species) and quaternary phosphonium compounds.

[0039] In certain embodiments, an effective supramolecular template comprises: (a) at least one of an aromatic quaternary ammonium compound, a branched alkyl chain quaternary ammonium compound, an alkylbenzene sulfonate, an alkylbenzene phosphonate, an alkylbenzene carboxylate, or a substituted phosphonium cation; and (b1) a constituent group containing at least one of an organosilane, a hydroxysilyl, an alkoxysilyl, an aromatic, a branched alkyl, a sulfonate, a carboxylate, or a phosphate as a head group; or (b2) a constituent group containing at least one of an organosilane, a hydroxysilyl, an alkoxysilyl, an aromatic, a branched alkyl, a sulfonate, a carboxylate, or a phosphate as a tail group. In certain embodiments, an effective supramolecular template comprises a sulfonate group (non-limiting examples include sulfonated bis(2-hydroxy-5-dodecylphenyl)methane (SBHDM)). In certain embodiments, an effective supramolecular template comprises a carboxylate group (non-limiting example is sodium 4-(octyloxy)benzoate). In certain embodiments, an effective supramolecular template comprises a phosphonate group (non-limiting example is tetradecyl(1,4-benzene)bisphosphonate). In certain embodiments, an effective supramolecular template comprises an aromatic group (non-limiting example is cetyl dimethyl benzyl ammonium chloride). In certain embodiments, an effective supramolecular template comprises an aliphatic group (non-limiting example is tetraoctylammonium chloride).

[0040] The supramolecular template is provided as a cation / anion pair. In certain embodiments, the cation of the supramolecular template is as described above, and pairs with a selected anion such as Cl - Br - OH - F - and I - etc. In certain embodiments, the cation of the supramolecular template is as described above, and Cl - Br - or OH -It pairs with anions such as. In certain embodiments, an effective supramolecular template includes dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (commonly abbreviated as "TPOAC"), or a derivative of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. In certain embodiments, an effective supramolecular template includes dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, or a derivative of dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. In certain embodiments, an effective supramolecular template includes [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilylpropyl)-dimethylammonium iodide, or a derivative of [2,3-bis(dodecanoyloxy)-propyl](3-(trimethoxysilylpropyl)-dimethylammonium iodide).

[0041] In certain embodiments, the system includes an effective amount of an ionic cosolute (i.e., in addition to the anion paired with the supramolecular template). In certain embodiments where an ionic cosolute is used, it is provided at a concentration in the aqueous suspension of about 0.01 - 0.5 M. In certain embodiments where an ionic cosolute is used, it is provided at a concentration in the aqueous suspension of about 0.01 - 5 wt%. In certain embodiments, the ionic cosolute is selected from the group consisting of CO3 2- 、SO4 2- 、S2O3 2- 、H2PO4 - 、F - 、Cl - 、Br - 、NO3 - 、I - 、ClO4 - 、SCN - 、and C6H5O8 -3 (citrate). In certain embodiments, the ionic cosolute is selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles to provide the desired hexagonal mesophase symmetry. In certain embodiments, sulfate (SO4 2-) is an ionic cosolute selected based on the Hofmeister series / lyotropic series to control the curvature / shape of the micelles so as to result in a hierarchical ordered CMM having a defined long-range mesoporous order with hexagonal mesophase symmetry; in certain embodiments where sulfate is used as the ionic cosolute, sulfate salts such as ammonium sulfate or metal sulfates are used, and this metal can be an alkali metal, alkaline earth metal, transition metal, noble metal, or rare earth metal.

[0042] The present disclosure is applicable to various types of CMMs as parent materials, including zeolites or zeolite-type materials. In certain embodiments, the parent CMM exhibits both good crystallinity and Al distribution in order to obtain high-quality HOCMM while maintaining composite phases and / or impurities.

[0043] Zeolite materials suitable as parent CMMs are the identifiers ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV, EUO, EWO, EWS, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFT, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POR, POS, PSI, PTO, PTT, PTY, PUN, PWN, PWO, PWW, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SOD, SOF, SOR, SOS, SOV, SSF, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN,YFI, YUG, ZON, * BEA, * CTH, * -EWT, * -ITN, * MRE, * PCS, * SFV, * -SSO, * STO, * -SVY, and * including those having UOE, including those identified by the International Zeolite Association. For example, certain zeolites known to be useful in the petroleum refining industry include, but are not limited to, AEI, * BEA, CHA, FAU, MFI, MOR, LTL, LTA, or MWW. In certain embodiments, the parent zeolite can be a (FAU) framework zeolite including, for example, USY having a micropore diameter related to a 12-membered ring as seen along the

[0111] direction of 7.4×7.4 Å. In certain embodiments, the parent zeolite can be a (MFI) framework zeolite including, for example, ZSM-5 having micropore diameters related to 10-membered rings as seen along the

[0100] and

[0010] directions of 5.5×5.1 Å and 5.6×5.3 Å, respectively. In certain embodiments, the parent zeolite can be a (MOR) framework zeolite including, for example, mordenite zeolite having micropore diameters related to 12-membered and 8-membered rings as seen along the

[0001] and

[0001] directions of 6.5×7.0 Å and 2.6×5.7 Å, respectively. In certain embodiments, the parent zeolite can be, for example, zeolite beta polymorph A having a micropore diameter related to a 12-membered ring as seen along the

[0100] and

[0001] directions of 6.6×6.7 Å and 5.6×5.6 Å, respectively, ( *BEA) It can be a framework zeolite. In certain embodiments, the parent zeolite can be, for example, a chabazite zeolite (CHA) framework zeolite including a micropore diameter related to an 8-membered ring when viewed perpendicular to the

[0001] direction, such as 3.8×3.8 Å. In certain embodiments, the parent zeolite can be, for example, a Linde type L zeolite (zeolite L) (LTL) framework zeolite including a micropore diameter related to a 12-membered ring when viewed along the

[0001] direction, such as 7.1×7.1 Å. In certain embodiments, the parent zeolite can be, for example, a Linde type A zeolite (zeolite A) (LTA) framework zeolite including a micropore diameter related to an 8-membered ring when viewed along the

[0100] direction, such as 4.1×4.1 Å. In certain embodiments, the parent zeolite can be, for example, an (AEI) framework zeolite having a micropore diameter related to an 8-membered ring when viewed perpendicular to the

[0001] direction, such as 3.8×3.8 Å. In certain embodiments, the parent zeolite can be, for example, an MCM-22 (MWW) framework zeolite including micropore diameters related to 10-membered rings when viewed perpendicular to the

[0001] direction of "interlayer" and "intralayer" of 4.0×5.5 Å and 4.1×5.1 Å, respectively.

[0044] In certain embodiments, the parent CMM is a zeolite-type material, such as aluminophosphate (AlPO), silicon-substituted aluminophosphate (SAPO), or metal-containing aluminophosphate (MAPO). In certain embodiments, the parent CMM is a zeolite-based silicon-only framework material.

[0045] As described above, embodiments of the present specification include supramolecular templates containing one or more bulk-like groups having dimensions based on modeling of molecular dimensions as rectangular parallelepipeds having dimensions A, B, and C using van der Waals radii for each individual atom, and one or more, two or more, or all three of the dimensions A, B, and C are such that their dimensions are sufficiently close or their dimensions are sufficiently large that they limit diffusion into the micropores of the CMM. Also, as already mentioned with respect to known parameters related to pore dimensions for exemplary zeolites, such parameters affect the selection of the supramolecular template. For example, in the examples herein, FAU zeolite was used; when the supramolecular template material was CTAB (about 0.25 nm), HOCMM was not realized; however, when the supramolecular template was an organosilane (about 0.7 nm), HOCMM was realized because these dimensions are close to the pore dimensions of the FAU zeolite and thus their entry into such pores is restricted. Similarly, a suitable supramolecular template is determined based on the selected parent CMM.

[0046] In certain embodiments, the parent CMM used in the method is a zeolite of the present specification having an SAR suitable for a particular type of zeolite. Generally, the SAR of the parent zeolite can be in the range of about 2 to 10000, 2 to 5000, 2 to 500, 2 to 100, 2 to 80, 5 to 10000, 5 to 5000, 5 to 500, 5 to 100, 5 to 80, 10 to 10000, 10 to 5000, 10 to 500, 10 to 100, 10 to 80, 50 to 10000, 50 to 5000, 50 to 1000, 50 to 500, or 50 to 100. In certain embodiments, the SAR of the parent zeolite is greater than or equal to 5 or 10 to achieve long-range order. In embodiments where the SAR is less than 10, uniform mesoporosity and a certain degree of order can be achieved and the amorphous framework material remains in the product.

[0047] Figures 1 and 2 are schematic diagrams of a method for making the compositions disclosed herein that use hierarchical ordering by a post-synthetic ensemble synthesis pathway, including a general synthetic mechanism of how AHE affects the g-value to change the curvature of micelles and induce a mesophase transition. The CMMs schematically shown in Figures 1 and 2 are FAU zeolites, but it is understood that other CMMs can be used as the parent CMMs to form the compositions herein by a post-synthetic ensemble synthesis pathway.

[0048] The method includes base-mediated decomposition / cleavage of the parent CMM into oligomeric components and reorganization into a hierarchical ordered mesostructure by supramolecular templating and, in certain embodiments, by the Hofmeister effect. The parent CMM 10 is provided in a crystalline form. An effective amount of an alkaline reagent and an effective amount of a surfactant are added with respect to supramolecular templating to form an aqueous suspension, which suspension is maintained under hydrothermal conditions to form oligomeric CMM units 12 of the parent CMM (such as oligomeric zeolite units when the parent CMM is a zeolite). The supramolecular template molecules 14 are formed into shaped micelles 16, and the oligomeric CMM units hierarchically reassemble and crystallize around the shaped micelles to form an ordered mesostructure, HOCMM 18, having defined symmetric mesopores 20 and mesopore walls formed of oligomeric CMM units, whereby the micropores 22 of the CMM structure underlying the parent CMM are retained. In certain embodiments, the compositions herein are HOCMMs 18 containing shaped micelles 16. In certain embodiments, the compositions herein are HOCMMs 18 having surfactants 14 formed on shaped micelles 16 that are removed by chemical methods such as, for example, solvent extraction, chemical oxidation, or ionic liquid treatment; or physical methods such as calcination, supercritical CO2, microwave-assisted treatment, ultrasonic-assisted treatment, ozone treatment, or plasma technology.

[0049] The distinct mesophase transitions of hierarchical assemblies that result in distinct mesostructures may be due to the synergistic action of the anionic Hofmeister effect (ion-specific interactions) in supramolecular self-assembly. Anions of various sizes and charges possess various polarizabilities, charge densities, and hydration energies in aqueous solution. When paired with the positive surfactant head groups, these properties can affect the electrostatic repulsion between the head groups and the hydration of the micelle interface, and thus change the head group area (a0). Such short-range ion-specific interactions can be a significant driving force in changing the curvature of micelles and inducing mesophase fibers.

[0050] Referring to FIG. 2, a schematic synthesis mechanism is shown that includes a schematic diagram of the effect of the g-value and simultaneously the micelle curvature and the induced mesophase transition on the AHE. The molar ratio of the surfactant to the cosolute (which can be expressed as the molar ratio of the surfactant salt) is effective in generating the desired mesophase structure. The molar ratio of the surfactant to the cosolute is selected to provide a surfactant packing parameter suitable for inducing a mesophase transition to a desired geometry that induces a change in the curvature of the micelle. In certain embodiments, sulfate is used as the ionic cosolute, the micelle curvature is represented by a surfactant packing parameter g of about 1 / 2, or about 0.4 - 0.6, or 0.5, and the resulting HOCMM has a long-range mesoporous order of hexagonal symmetry. For example, in certain embodiments, the molar ratio of the surfactant to the cosolute for synthesizing an HOCMM having a long-range mesoporous order of hexagonal symmetry may be in the range of about 0.8 - 1.3, 0.9 - 1.3, 0.9 - 1.2, or 0.8 - 1.2. The ion-specific interaction (Hofmeister effect) on the micelle curvature in the self-assembly process is evident. Anions of various sizes and charges carry various polarizabilities, charge densities, and hydration energies in aqueous solutions. When paired with the positive surfactant head group, these properties can affect the electrostatic repulsion between the head groups and the hydration at the micelle interface, and thus the area of the head group (a0) changes. Such short-range ion-specific interactions can be a significant driving force in changing the micelle curvature and inducing a mesophase transition. Hofmeister series (SO4 2- > HPO4 2- > OAc - > Cl - > Br - > NO3 - > ClO4 - > SCN -Based on [[ID=]], strongly hydrated ions (on the left side of the series) can increase the micelle curvature, while weakly hydrated ions can reduce the micelle curvature. Without being bound by theory, the influence of cosolutes such as salts in the mesophase order may be due to its charge balancing effect; in surfactant self-assembly, due to the hydrophobic effect, high-density surfactant molecules are tightly packed within the micelle; as a result, the electrostatic repulsion of the charged head groups should be minimized by counteranions to avoid inducing easy aggregation; thus, the auxiliary counteranions play a role in stabilizing the micelle despite the stepwise change in the concentration of the polyanionic zeolite component.

[0051] An effective amount of solvent is used in the process. In certain embodiments, the solvent is water. In certain embodiments, the solvent is water in the presence of a cosolvent selected from the group consisting of polar solvents, nonpolar solvents, and pore swelling agents (such as 1,3,5-trimethylbenzene). In certain embodiments, the solvent is selected from the group consisting of polar solvents, nonpolar solvents, and pore swelling agents (such as 1,3,5-trimethylbenzene) in the absence of water. In an embodiment, the mixture components are added to the reaction vessel together with water and then heated. Typically, water allows for proper mixing to achieve a more homogeneous distribution of the suspended components and ultimately produces a more desirable product as the properties of each crystal match more closely with those of adjacent crystals. Insufficient mixing may result in an undesirable product with an amorphous phase or a lower degree of long-range order.

[0052] The suspension components are combined in any suitable order and thoroughly mixed to form a homogeneous distribution of the suspended components. The suspension can be maintained under autogenous pressure (from the components or with the addition of a gas purge into the tank before heating the components), in an autoclave, or in another suitable tank under agitation, tumbling, and / or shaking, etc. The mixing of the suspension components is carried out at a temperature between about 20 - 60, 20 - 50, or 20 - 40 °C.

[0053] The cutting and reassembly steps are carried out during the hydrothermal treatment to form solids (products, HOCMMs with a defined long-range mesoporous order of 2D hexagonal symmetry) suspended in the supernatant (mother liquor). The hydrothermal treatment is carried out over a period of about 4 to 168, 12 to 168, 24 to 168, 4 to 96, 12 to 96, or 24 to 96 hours; at a temperature of about 70 to 250, 70 to 210, 70 to 180, 70 to 160, 70 to 150, 90 to 250, 90 to 210, 90 to 180, 90 to 160, 90 to 150, 110 to 250, 110 to 210, 110 to 180, 110 to 160, or 110 to 150 °C; and at a pressure from approximately atmospheric pressure to autogenous pressure. In certain embodiments, the hydrothermal treatment is carried out in the same tank used for mixing, or the suspension is transferred to another tank (such as another autoclave or low-pressure tank). In certain embodiments, the tank used for the hydrothermal treatment is stationary. In certain embodiments, the tank used for the hydrothermal treatment is in a stirred state sufficient to suspend the components.

[0054] The HOCMMs with a 2D hexagonal symmetry and a defined long-range mesoporous order are the products to be recovered. The solids are recovered using known techniques such as centrifugation, decantation, gravity, vacuum filtration, filter press, or rotary drum. The recovered HOCMMs with a 2D hexagonal symmetry and a defined long-range mesoporous order are dried at a temperature of, for example, about 50 to 150, 50 to 120, 80 to 150, or 80 to 120 °C for about 0.5 to 96, 12 to 96, or 24 to 96 hours under atmospheric or vacuum conditions.

[0055] In certain embodiments, the dried HOCMM having a defined long-range mesoporous order of 2D-hexagonal symmetry is calcined to remove, for example, the mesophase-surviving supramolecular template and other constituents from the mesopores and / or the individual zeolite cell micropores. The conditions regarding the calcination of the embodiments carried out can include a temperature in the range of about 350 - 650, 350 - 600, 350 - 550, 500 - 650, 500 - 600, or 500 - 550 °C, under atmospheric pressure or vacuum, and a period of about 2.5 - 24, 2.5 - 12, 5 - 24, or 5 - 12 hours. The calcination can be carried out at a rate of increase in the range of about 0.1 - 10, 0.1 - 5, 0.1 - 3, 1 - 10, 1 - 5, or 1 - 3 °C per minute. In certain embodiments, the calcination can have a first step of raising the temperature to a temperature between 100 - 150 °C and having a holding time of about 1.5 - 6 or 1 - 12 hours (the rate of increase being about 0.1 - 5, 0.1 - 3, 1 - 5, or 1 - 3 °C per minute), and then raising to a higher temperature and having a final holding time in the range of about 1.5 - 6 or 1 - 12 hours.

[0056] In certain embodiments, the supernatant remaining after recovering the product from the system can be recovered and all or a portion thereof reused as all or a portion of the solution in a subsequent process for synthesizing a HOCMM or another HOCMM having a defined long-range mesoporous order of 2D-hexagonal symmetry. In this embodiment, the recovered supernatant used in the subsequent process is referred to as the supernatant from a conventional synthesis. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent alkaline reagent (e.g., urea). In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent supramolecular template. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent ionic cosolute. In certain embodiments, the new synthesis can be performed using the supernatant from a conventional synthesis together with the parent CMM and an additional amount of a constituent alkaline reagent (e.g., urea) and / or a constituent supramolecular template and / or, optionally, a constituent ionic cosolute.

[0057] The compositions recovered as described herein are hierarchical ordered CMMs (such as zeolites) having a defined long-range mesoporous order with 2D-hexagonal symmetry. These are characterized by the mesoporous channel direction defined by the CMM micropore channels within the walls of the mesostructure. The HOCMMs having a defined long-range mesoporous order, recovered from synthesis, retain the supramolecular template described herein in the mesopores (i.e., prior to calcination or extraction of the supramolecular template). In certain embodiments, the HOCMMs having a defined long-range mesoporous order with 2D-hexagonal symmetry, recovered from synthesis, retain micelles of the supramolecular template described herein within the mesopores (i.e., prior to calcination or extraction of the supramolecular template). The recovered compositions described herein retain the structural integrity of the microporous zeolite structure by controlled cleavage of the parent zeolite and subsequent controlled reassembly of the zeolite oligomers under controlled micelle curvature, resulting in HOCMMs having a defined mesoporous 2D-hexagonal symmetry.

[0058] This defined long-range mesoporosity is difficult to understand in the field of hierarchical ordered zeolites. The long-range order is defined by secondary peaks associated with the periodic arrangement of the mesopores in the x-ray diffraction (XRD) pattern for a given mesophase, as demonstrated in the examples herein, and / or by microscopic observation. These peaks associated with the mesoporous properties of the product are observed at low 2θ angles. The material also exhibits high-angle peaks associated with zeolites, observed at high 2-theta angles. In certain embodiments, the low-angle peaks refer to those occurring at 2θ angles of less than about 6°.

[0059] In certain embodiments herein, the long-range mesoporous order of the HOCMMs generated by the methods described herein is characterized by the periodicity of the mesopores repeating over a length greater than about 50 nm.

[0060] In certain embodiments, the HOCMM having the defined long-range mesoporous order of 2D-hexagonal symmetry herein has a surface area of about 200 - 1500, 200 - 1000, 200 - 900, 400 - 1500, 400 - 1000, 400 - 900, 500 - 1500, 500 - 1000, or 500 - 900 m² / g. In the embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-hexagonal symmetry herein has a mesoporous pore diameter of about 2 - 50, 2 - 20, or 2 - 10 nm. In the embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-hexagonal symmetry herein has a silica-to-alumina ratio of about 2.5 - 1500, 3 - 1500, 4 - 1500, 5 - 1500, 6 - 1500, 2.5 - 1000, 3 - 1000, 4 - 1000, 5 - 1000, 6 - 1000, 2.5 - 500, 3 - 500, 4 - 500, 5 - 500, 6 - 500, 2.5 - 100, 3 - 100, 4 - 100, 5 - 100, or 6 - 100. In the embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-symmetry herein has a total pore volume of about 0.01 - 1.50, 0.01 - 1.0, 0.01 - 0.75, 0.01 - 0.65, 0.1 - 1.50, 0.1 - 1.0, 0.1 - 0.75, 0.1 - 0.65, 0.2 - 1.50, 0.2 - 1.0, 0.2 - 0.75, 0.2 - 0.65, 0.3 - 1.50, 0.3 - 1.0, 0.3 - 0.75, or 0.3 - 0.65 cc / g. 2 / g. In the embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-hexagonal symmetry herein has a mesoporous pore diameter of about 2 - 50, 2 - 20, or 2 - 10 nm. In the embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-hexagonal symmetry herein has a silica-to-alumina ratio of about 2.5 - 1500, 3 - 1500, 4 - 1500, 5 - 1500, 6 - 1500, 2.5 - 1000, 3 - 1000, 4 - 1000, 5 - 1000, 6 - 1000, 2.5 - 500, 3 - 500, 4 - 500, 5 - 500, 6 - 500, 2.5 - 100, 3 - 100, 4 - 100, 5 - 100, or 6 - 100. In the embodiments herein, the HOCMM having the defined long-range mesoporous order of 2D-symmetry herein has a total pore volume of about 0.01 - 1.50, 0.01 - 1.0, 0.01 - 0.75, 0.01 - 0.65, 0.1 - 1.50, 0.1 - 1.0, 0.1 - 0.75, 0.1 - 0.65, 0.2 - 1.50, 0.2 - 1.0, 0.2 - 0.75, 0.2 - 0.65, 0.3 - 1.50, 0.3 - 1.0, 0.3 - 0.75, or 0.3 - 0.65 cc / g.

[0061] In the embodiments of this specification, the products generated and demonstrated by the above method in the examples of this specification are characterized by a mesophase having hexagonal symmetry. In certain embodiments, the product is a 2D-hexagonal ordered mesoporous zeolite. The HOCMM with a mesophase having hexagonal symmetry is characterized by the hexagonal mesoporous channel direction with CMM micropore channels within the walls of the mesostructure. The hexagonal mesophase can possess one of p6m, p6mm, or p63 / mmc symmetry. In the embodiments of this specification, the hexagonal mesophase possesses p6mm symmetry, and the secondary XRD peaks related to the periodic arrangement configuration of the mesopores are present in one or more of the (11) and (20) reflections. In the embodiments of this specification, the hexagonal mesophase possesses p6mm symmetry, and the secondary XRD peaks are present in both the (11) and (20) reflections. In the embodiments of this specification, the hexagonal mesophase possesses p6mm symmetry, and the advanced long-range hexagonal p6mm mesophase order is observable by microscopy looking at electron beams perpendicular to the pores along the

[0110] zone axis and / or parallel to the pores along the

[0001] zone axis. In these embodiments, the CMM structure is arranged and configured in hexagonal p6mm symmetry at the mesoscale, and the CMM particles (regardless of their atomic-level symmetry or structure) are arranged and configured around the micelles (at the mesoscale), whereby micelles exhibiting hexagonal symmetry are arranged and configured. Thus, the HOCMM having a hexagonal p6mm mesophase is a CMM characterized by atomic-level symmetry and possessing micropores specific to that type of CMM, including those arranged and configured in hexagonal p6mm symmetry at the mesoscale level together with the mesopores, and the walls of the mesopores and a group of mesostructures between the mesopores are characterized by the said CMM (e.g., crystalline zeolite). This is created as described herein by forming oligomers of the underlying CMM and arranging and configuring those oligomers around micelles exhibiting hexagonal symmetry at the mesoscale.In one embodiment, the HOCMM is provided that includes an MFI zeolite having an orthorhombic symmetry at the atomic level arranged and configured in a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent MFI zeolite, oligomers of the parent MFI zeolite are formed and arranged around micelles exhibiting hexagonal symmetry at the mesoscale. In one embodiment, the HOCMM is provided that includes a CHA zeolite having a trigonal symmetry at the atomic level arranged and configured in a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent CHA zeolite, oligomers of the parent CHA zeolite are formed and arranged around micelles exhibiting hexagonal symmetry at the mesoscale. In one embodiment, the HOCMM is provided that includes a BEA zeolite having a tetragonal symmetry at the atomic level arranged and configured in a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent BEA zeolite, oligomers of the parent BEA zeolite are formed and arranged around micelles exhibiting hexagonal symmetry at the mesoscale. In one embodiment, the HOCMM is provided that includes an MWW zeolite having a hexagonal symmetry at the atomic level arranged and configured in a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent MWW zeolite, oligomers of the parent MWW zeolite are formed and arranged around micelles exhibiting hexagonal symmetry at the mesoscale. In one embodiment, the HOCMM is provided that includes a FAU zeolite having a cubic symmetry at the atomic level arranged and configured in a hexagonal p6mm symmetry mesoscale. During the synthesis of the hierarchical ordered zeolite from the parent FAU zeolite, oligomers of the parent FAU zeolite are formed and arranged around micelles exhibiting hexagonal symmetry at the mesoscale.

[0062] The HOCMM produced according to the present disclosure is effective as a catalyst or a catalyst component in the hydrocracking of hydrocarbon oils. In certain embodiments, provided herein is a method for hydrocracking a hydrocarbon oil, the method comprising hydrocracking the hydrocarbon oil with a hydrocracking catalyst comprising a hierarchically ordered zeolite produced according to the present disclosure. In certain embodiments, provided herein is a method for hydrocracking a hydrocarbon oil, the method comprising hydrocracking the hydrocarbon oil with a hydrocracking catalyst comprising a hierarchically ordered FAU zeolite produced according to the present disclosure. In certain embodiments, provided herein is a method for hydrocracking a hydrocarbon oil, the method comprising hydrocracking the hydrocarbon oil with a hydrocracking catalyst comprising a hierarchically ordered crystalline microporous material having a hexagonal symmetric defined long-range mesoporous order including mesopores with walls of a crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material.

[0063] The HOCMM according to the present disclosure is effective as a catalyst or a catalyst component in the hydrocracking of hydrocarbon oils. The HOCMM can be used as a support on which one or more active and durable components are loaded on the surface as a hydrocracking catalyst. The active metal component is loaded on a surface including the mesopore wall surface, the micropore wall surface, or the mesopore and micropore wall surfaces, and is held, for example; the active metal component is loaded according to known methods such as providing an aqueous solution of the active metal component and subjecting the HOCMM as a catalyst support material to immersion, incipient wetness, and evaporation, or any other suitable method. In certain embodiments, the CMM of the HOCMM comprises zeolite. In certain embodiments, the CMM of the HOCMM comprises one or more zeolite types AEI, * BEA, CHA, FAU, MFI, MOR, LTL, LTA, or MWW. In certain embodiments, the CMM of the HOCMM comprises FAU zeolite.

[0064] The content of HOCMM and the active metal component is appropriately determined according to the target. In certain embodiments, the hydrocracking catalyst contains HOCMM as a carrier and an inorganic oxide component typically as a binder and / or granulating agent. For example, the carrier particles (before loading one or more hydrocracking active metal components) can contain HOCMM in the range of about 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40 mass%, and the remaining content is an inorganic oxide. In certain embodiments, the carrier particles (before loading one or more hydrocracking active metal components) can contain HOCMM in the range of about 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40 mass%, and the remaining content is an inorganic oxide and one or more other zeolite-based materials.

[0065] As the inorganic oxide component, any material used in hydrocracking or other catalyst compositions in related technologies can be used. Examples thereof include 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, phosphorus-alumina-zirconia, alumina-zirconia-titania, and phosphorus-alumina-titania.

[0066] The active metal component can include one or more metals or metal compounds (oxides or sulfides) known in the field of hydrocracking, including those selected from Groups 6, 7, 8, 9, and 10 of the IUPAC periodic table. In certain embodiments, the active metal component is one or more of Mo, W, Co, or Ni (oxides or sulfides). Additional active metal components can be contained in the catalyst in effective concentrations. For example, the total active component content in the hydrocracking catalyst can be present in amounts known in the relevant art, e.g., about 0.01 - 40, 0.1 - 40, 1 - 40, 2 - 40, 5 - 40, 0.01 - 30, 0.1 - 30, 1 - 30, 2 - 30, 5 - 30, 0.01 - 20, 0.1 - 20, 1 - 20, 2 - 20, or 5 - 20 wt% with respect to the metal, oxide, or sulfide. In certain embodiments, the active metal component is loaded using a solution of the oxide and, prior to use, the hydrocracking catalyst is sulfided.

[0067] In certain embodiments, a method for hydrocracking a hydrocarbon oil using the hydrocracking catalyst described herein, including HOCMM as a component, is carried out in the presence of hydrogen at a reactor temperature in the range of, for example, about 370 - 833, 370 - 816, 370 - 650, 375 - 833, 375 - 816, or 375 - 650 °C for a hydrocarbon oil having a boiling point in the range of, and a hydrogen partial pressure in the range of about 20 - 100, 20 - 70, 20 - 55, 30 - 100, 30 - 70, 30 - 55, or 40 - 55 bar, a liquid hourly space velocity (``LHSV'', the value obtained by dividing the volume flow rate of the liquid feed by the volume of the catalyst) in the range of about 0.1 - 10, 0.2 - 1.5 h -1 and a hydrogen (Nm 3 / m 3) including the step of introducing into a hydrocracking zone that includes a hydrogen / oil ratio that is [as described]. The "hydrocracking zone" means one or more reactors and associated effluent separation equipment and can accommodate two or more reactors. In certain embodiments, the feedstock is pretreated within the boiling range described above or is a recycle stream, and its sulfur content is less than 100 ppmw or 50 ppmw or 10 ppmw, and its nitrogen content is less than 100 ppmw or 50 ppmw or 10 ppmw.

[0068] In a method for hydrocracking a hydrocarbon oil according to certain embodiments herein, the fluidized reactor described above can be a fluidized reactor selected from a stirred bath reactor, a fluidized bed reactor, a baffled slurry bath reactor, a fixed bed reactor, a rotary tube reactor, and a slurry bed reactor.

[0069] In a method for hydrocracking a hydrocarbon oil according to certain embodiments herein, the hydrocarbon oil described above preferably contains (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sand, (5) shale oil, (6) coal liquid, (7) plastic pyrolysis oil, (8) biomass-derived oil, or (9) heavy hydrocarbon oil obtained from Fisher-Tropsch wax.

[0070] In a method for hydrocracking a hydrocarbon oil according to certain embodiments of the present specification, the above-mentioned hydrocarbon oil contains a heavy hydrocarbon oil obtained from crude oil, synthetic crude oil, bitumen, oil sand, shale oil, or coal liquid, and the heavy hydrocarbon oil is preferably a) vacuum gas oil (VGO), b) deasphalted oil (DAO) or demetallized oil obtained from a solvent deasphalting process, c) light coker gas oil or heavy coker gas oil obtained from a coking process, d) cycle oil obtained from a fluid catalytic cracking (FCC) process, e) gas oil obtained from a bis-breaking process, or f) any of the recycle streams obtained from hydrocracking one or more of (a) to (e). In a method for hydrocracking a hydrocarbon oil according to certain embodiments of the present specification, the hydrocarbon oil includes a recycle stream obtained from hydrocracking of VGO. In a method for hydrocracking a hydrocarbon oil using a hydrocracking catalyst described herein and including HOCMM as a component according to certain embodiments of the present specification, the hydrocarbon oil includes a recycle stream obtained from hydrocracking of VGO, straight-run VGO, or pretreated straight-run VGO, and the selectivity to its naphtha and / or middle distillate is prepared as a function of the mesophase induced by the HOCMM described herein to enable operational flexibility. In a method for hydrocracking a hydrocarbon oil using a hydrocracking catalyst described herein and including HOCMM as a component according to certain embodiments of the present specification, the hydrocarbon oil is a recycle stream obtained from hydrocracking of VGO, straight-run VGO, or pretreated straight-run VGO, and includes one in which the selectivity to its naphtha and / or middle distillate is adjusted as a function of the mesophase induced by the HOCMM described herein to enable operational flexibility.

[0071] In a process for hydrocracking a hydrocarbon oil using a hydrocracking catalyst described herein, which includes HOCMM as a component according to certain embodiments herein, the hydrocarbon oil is a recycle stream obtained from hydrocracking of VGO, straight-run VGO, or pretreated straight-run VGO, and the selectivity to naphtha thereof is adjusted as a function of a hexagonal symmetry mesophase induced by the HOCMM described herein so as to enable operational flexibility.

Examples

[0072] The HOCMM produced in the examples herein exhibits a significant degree of defined long-range mesoporous order as given by the low-angle XRD pattern. The parent zeolites used in the examples and comparative examples possess the FAU framework, and zeolite Y (obtained from Zeolyst International, product name CBV 720) is referred to herein as zeolite HY-15 and has an SiO2 / Al2O3 (SAR) of about 30 (Si / Al atomic ratio of 15). The examples are shown with respect to this particular zeolite, but the methods herein can be applied to other sources and other types of parent CMMs obtained from different synthesis processes or from commercial manufacturers. Thus, the resulting compositions have a mesoporous structure with microporosity and CMM structure corresponding to the parent CMM. The solutions were prepared at room temperature (RT) under stirring at 500 RPM.

[0073] Characterization in this specification was carried out as follows. The powder X-ray diffraction pattern was obtained using a Bruker D8 diffractometer operating at 40 kV and 40 mA with Cu Kα radiation (λ = 0.154 nm) and a step size of 0.02°. N2 physical adsorption measurements were performed at 77 K using a Micrometrics ASAP 2420 instrument. All samples were degassed at 350 °C for 12 hours prior to analysis. The specific surface area and pore size distribution were calculated using the Brunauer-Emmett-Teller (BET) and non-local density functional theory (NLDFT) models. The micropore volume was calculated using the t-plot method. High-resolution transmission electron microscopy (TEM) studies were conducted using an FEI-Titan ST electron microscope operating at 300 kV. Scanning electron microscopy (SEM) images were obtained using a Nova Nano HR-SEM 240 microscope operating at 4 kV. The samples were sputter-coated with platinum (Pt) prior to analysis to eliminate the charging effect. The Si / Al ratio was calculated by solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) experiments using a Bruker Advance 400 MHz instrument applying a 4 μs high-frequency pulse and a 60 s recycle delay. Conversely, the bulk Si / Al ratio of the zeolite was calculated from an analysis performed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) using a 5100 ICP-OES Agilent instrument. Prior to analysis, the samples were mixed with hydrofluoric acid (HF) and nitric acid (HNO3) and decomposed at 260 °C and 160 bar using an Ultra WAVE microwave digestion system (Milestone).

[0074] For the acquisition of electron micrographs for tomography reconstruction, zeolite powder was deposited on a Quantifoil 300 mesh TEM grid supporting a continuous carbon film with a thickness of 2 nm on a perforated carbon film. Before the zeolite deposition, a dilute solution of gold nanoparticles (AuNPs) with a diameter of about 5 nm was dispersed on the TEM grid. The AuNPs were to be used for the alignment of the tomography serial tilt images. To protect the specimen from radiation-induced damage during the long exposure time required for tomography data acquisition, the acquisition of the tomography serial tilt images was performed on a Krios G4 (ThemoFisher (trademark)) electron microscope at liquid nitrogen temperature. The actual temperature at the stage level was about 183 °C. The serial tilt images were acquired in energy filter (EF) mode using a 30 eV slit to increase the contrast of the bright-field TEM images. Detection was performed with a Falcon i electron direct detector camera operating in electron counting mode with a 4096 pixel frame size. To keep the total exposure dose low, only sample tracking was performed after each serial tilt image during data acquisition. Refocusing was done manually about every 10 images. The angular range was ±64°, and the tilt step was 1°. The serial tilt images were aligned with IMOD software using 13 AuNPs as fiducial markers that were clearly visible at each tilt. Before reconstruction, image binning 2 was performed to increase the SNR and reduce the calculation time. To enhance the visibility of pores in the 3D tomogram, the images were filtered using an average background subtraction filter (ABSF) implemented as a script in Digital Micrograph. The SIRT reconstruction algorithm was executed with 100 iterations using a relaxation factor of 1.

[0075] Coke quantification was performed from thermogravimetric-temperature programmed oxidation (TG-TPO / MS) equipped with a mass spectrometer using a Mettler-Toledo TGA instrument. Before combustion, the catalyst sample was heated to 350 °C at a heating rate of 10 °C / min for 0.5 h under a N2 flow (50 mL / min). After cooling to 100 °C, coke combustion was carried out in air up to 850 °C at a heating rate of 5 °C / min. At the same time, a CO2 (m / z = 44) profile from combustion was analyzed using an OmniStarTM mass spectrometer (MS).

[0076] (Example 1A) An amount of 2.4 grams of NH4OH was added to 28.3 grams of water while stirring. An amount of 1.0 gram of dry zeolite HY-15 was dispersed in this solution and stirred for an additional 0.25 h. Then an amount of 0.4 gram of CTAB was added and stirred for an additional 0.5 h. The resulting solution was stirred for a further 1 h and then subjected to hydrothermal treatment at 130 °C for 24 h. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 h. The synthesized product was calcined in air at 550 °C for 6.0 h at a heating rate of 60 °C / h to obtain AH-CT (where AH refers to ammonium hydroxide and CT refers to CTAB). The AH-CT synthesized according to this procedure exhibited disordered mesoporosity and was characterized in FIGS. 3A - 4B and Table 3.

[0077] In an alternative procedure, an amount of 2.0 grams of dry zeolite HY-15 was dispersed in 56.6 grams of water while constantly stirring. To this solution, 0.77 gram of cetyltrimethylammonium bromide (CTAB) was added and stirred for an additional 0.5 h. Then, 4.75 grams of aqueous ammonium hydroxide (30 mass%) was added dropwise to the mixture while stirring. The resulting solution was stirred for a further 0.5 h and then hydrothermally treated at 130 °C for 24 h. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 h. The synthesized product was calcined in air at 550 °C for 6 h at a heating rate of 60 °C / h to obtain AH-CT exhibiting disordered mesoporosity.

[0078] (Example 1B) Provided is a procedure for synthesizing a 2D-hexagonal ordered mesoporous FAU-type zeolite. An amount of 2.4 grams of NH4OH was added to 28.3 grams of water while stirring. An amount of 1.0 gram of dry zeolite HY-15 was dispersed in the base solution and further stirred for 0.25 hour. Then, an amount of 1.5 milliliters of dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium chloride (DOAC) (42.0 mass% in methanol) was added and further stirred for 0.5 hour. The resulting solution was further stirred for 1 hour, and then hydrothermal treatment was carried out at 130 °C for 24 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain AH-TMS (where TMS refers to DOAC, dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium chloride). The AH-TMS formed according to this procedure exhibits a 2D-hexagonal ordered mesoporous symmetry and is characterized in FIGS. 3A to 4B and Table 3.

[0079] In an alternative procedure, an amount of 2.0 grams of zeolite H-Y was dispersed in 56.6 grams of water while constantly stirring. To this solution, 3.0 milliliters of DOAC (42.0 mass% in methanol) was added and further stirred for 0.5 hour. Then, 4.75 grams of an aqueous ammonium hydroxide solution (30 mass%) was added dropwise to the mixture while stirring. The resulting solution was further stirred for 0.5 hour, and then hydrothermal treatment was carried out at 130 °C for 24 hours. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain AH-TMS. The AH-TMS formed according to this procedure possesses a 2D-hexagonal ordered mesoporous symmetry (as evident from the TEM images of this AH-TMS presented in FIGS. 5A to 5C).

[0080] (Example 2) A procedure for synthesizing 2D - hexagonal ordered mesoporous FAU - type zeolite is provided using sulfate as an ionic co - solute. An amount of 0.6 grams of urea was added to 10.0 grams of water to form a homogeneous solution. To this solution, an amount of 1.0 gram of dry zeolite HY - 15 was added and stirred for 0.5 hour. Then, 20 milliliters of water, 0.165 grams of ammonium sulfate ((NH4)2SO4), and 1.5 milliliters of DOAC (42.0 mass% in methanol) were added dropwise, and the mixture was stirred for a further 2 hours. The resulting solution was subjected to hydrothermal treatment at 130 °C for 72 hours. The obtained solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6.0 hours at a heating rate of 60 °C / hour to obtain U - S - TMS (where U refers to urea, S refers to sulfate, and TMS refers to DOAC). The U - S - TMS formed according to this procedure exhibits 2D - hexagonal ordered mesoporous symmetry, is characterized in FIGS. 6A - 6B, and its TEM images are presented in FIGS. 7A - 7E.

[0081] In an alternative procedure, an amount of 1.2 grams of urea was dissolved in 60.0 grams of water to form a homogeneous solution. To this mixture, an amount of 0.33 g of ammonium sulfate ((NH4)2SO4) was added as a source of ionic co - solute and stirred until homogeneous. To this mixture, 2.0 grams of dry zeolite HY - 15 was added and stirred for 10 minutes. Then, 3.0 milliliters of DOAC (42.0 mass% in methanol) was added. The resulting solution was stirred for 0.5 hour, and then hydrothermal treatment was carried out at 130 °C for 72 hours. The obtained solid was filtered, washed with water, and dried at 120 °C for 24 hours. The synthesized product was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C / hour to obtain U - S - TMS (where Y refers to zeolite Y, U refers to urea, S refers to sulfate, and TMS refers to dimethyloctadecyl(3 - trimethoxysilyl - propyl) - ammonium chloride), which possesses 2D - hexagonal ordered mesoporous symmetry.

[0082] In Example 1B, the resulting hierarchical zeolite is arranged in a hexagonal configuration as observed in the

[0100] and

[0110] directions, and is a 2D-hexagonal ordered mesoporous FAU-type zeolite having mesoporous channels with FAU micropore channels in the walls and a group of mesostructures between the mesopores. Figure 3A shows a low-angle XRD pattern, Figure 3B shows a high-angle XRD pattern, Figure 4A shows an N2 physisorption isotherm, and Figure 4B shows an NLDFT pore size distribution, where "a" corresponds to HY-15, "b" corresponds to AH-CT, and "c" corresponds to AH-TMS: Figures 5A to 5C are transmission electron microscopy (TEM) micrographs of AH-TMS showing hexagonal mesoporous channels in the

[0100] and

[0110] directions with respect to the FAU micropore channels in the walls of the mesostructure; Figure 5A shows a TEM micrograph at a scale of 50 nanometers; Figure 5B shows TEM micrographs in the

[0100] direction and the

[0110] direction at a scale of 20 nanometers, and also shows corresponding schematic diagrams and unit cell dimensions; Figure 5C shows a TEM micrograph in the

[0100] direction at a scale of 10 nanometers (with an overlapping schematic diagram of the underlying zeolite structure). The high degree of long-range order is evident from Figure 3A, and the low-angle XRD pattern "c" shows Bragg reflections at angles corresponding to the 100, 110, and 210 planes, which indicates hexagonal mesopore symmetry in AH-TMS. Conversely, the low-angle XRD pattern "b" shows disordered mesoporosity, despite having a uniform pore size distribution (PSD) from the corresponding N2 physisorption isotherm, due to heterogeneous zeolite decomposition and limited supramolecular self-assembly, as evident from Figures 3A and 4A. The retention of the underlying zeolite structure is evident from Figure 3B, and the high-angle XRD patterns are consistent with the parent zeolite, FAU zeolite, for all samples. Figures 4A and 4B show the N2 physisorption isotherm and the pore size distribution of the prepared zeolites. AH-TMS (shown as "c" in Figures 4A and 4B) demonstrates excellent hierarchical ordered mesoporosity, as indicated by a characteristic type-IV isotherm with H1 hysteresis. Furthermore, the high mesopore volume and narrow pore size distribution further confirm the presence of long-range ordered mesoporosity.

[0083] As-prepared and calcined products from Example 2 are characterized in Fig. 6A, and the calcined product from Example 2 is characterized in Fig. 6B. Fig. 6A shows a low-angle XRD pattern, and Fig. 6B shows a high-angle XRD pattern, the intensity of which is represented in arbitrary units (a.u.) plotted against the frequency 2θ (°), with the as-prepared pattern indicated by a dashed line and the calcined pattern indicated by a solid line. The high degree of long-range order of as-prepared and calcined U-S-TMS is evident from Fig. 6A, where the low-angle XRD pattern shows Bragg reflection peaks 100, 110, and 200, indicating a 2D-hexagonal ordered mesoporous symmetry. The retention of the underlying zeolite structure is evident from Fig. 6B, where the high-angle XRD pattern is consistent with that of the parent zeolite, the FAU zeolite. Figs. 7A - 7E present TEM micrographs of U-S-TEM synthesized in the first procedure of Example 2, including Fig. 7A in the

[0100] and

[0110] directions at a scale of 20 nanometers with a corresponding structural diagram, an enlarged view of a portion of Fig. 7A in the

[0100] direction with an inset of a fast Fourier transform pattern in Fig. 7B, Fig. 7C in the

[0110] direction at a scale of 50 nanometers showing selected area electron diffraction (SAED) in the inset, Fig. 7D in the

[0100] and

[0110] directions at a scale of 50 nanometers, and Fig. 7E in the

[0100] and

[0110] directions at 20 nanometers with a corresponding structural diagram.

[0084] According to the examples herein, a hierarchical ordered FAU-type framework showing 2D-hexagonal (p6mm) symmetry is prepared for the first time by systematic post-synthesis reassembly.

[0085] (Example 3) The catalytic properties of U-S-TMS 2D-hexagonal ordered mesoporous FAU-type zeolite were evaluated with respect to the hydrocracking of the recycle stream (feedstock for the second stage) from a two-stage hydrocracking unit using a fixed-bed reactor. The feedstock was pretreated straight-run vacuum gas oil from the first-stage hydrocracking unit and thus contained very low levels of sulfur and nitrogen at 40 ppmw and 17 ppmw, respectively. The composition and properties of the feedstock are summarized in Table 4. The catalyst was prepared by mixing mesoporous FAU-type zeolite (30%) with alumina (70 wt%), and then first wet-impregnating nickel (Ni) and molybdenum (Mo) species. In particular, 70 wt% of alumina was dispersed in a minimal amount of deionized (DI) water. To this slurry, 30 wt% of zeolite was slowly added and stirred for 15 minutes. In the next step, the desired amounts of (NH4)6Mo7O 24 ·4H2O (8.5 wt% Mo), Ni(NO3)2·6H2O (3.0 wt% Ni), and citric acid (7.5 wt%) were added to the zeolite-alumina slurry and stirred for an additional hour. The mixture thus obtained was dried overnight at 120 °C and then calcined at 550 °C for 4 hours. The resulting catalyst in the form of a powder charged with metal oxides was sulfided in a batch reactor (Parr) at 300 °C and 5 bar for 4 hours in the presence of 40 bar of hydrogen using dimethyldisulfide (1 mL / g of catalyst) as the sulfiding agent. The catalyst bed was prepared by filling 0.5 g of the sulfide catalyst between two layers of silicon carbide (46 mesh) (volume 16 ml) in a stainless-steel cylindrical reactor (SS316; inner diameter - 9.2 mm; length - 300 mm) with a 20-μm porous plate positioned at the bottom. The charged catalyst was purged with a H2 / N2 (volume ratio 75:25) gas mixture at a flow rate of 100 ml / h and at 450 °C and 50 bars for 2 hours to remove any moisture. The catalyst study was carried out at a temperature of 400 °C and a pressure of 50 bar with a H2 / oil ratio of 750 Nm 3 / m 3 and a weight hourly space velocity (WHSV) of 1 h -1It was carried out in a state where it is. The reaction was carried out for 10 hours, the liquid was separated from the liquid-gas separator, and collected periodically every hour and subjected to gas chromatography (GC) analysis. The liquid product was analyzed according to the ASTM D2887 standard test method using an Agilent 6980N GC connected to simulated distillation (SIMDIS) software.

[0086] The conversion rate (X) of the feedstock, the selectivity (S) and yield (Y) for the desired hydrocarbon mixture, naphtha (C4-150 °C), kerosene (150-250 °C), and gas oil (250-370 °C) were calculated from the boiling point distribution curves obtained by literature-based SIMDIS analysis according to equations (1), (2), and (3), respectively:

[0087]

Number

[0088] where

[0089]

Number

[0090] corresponds to the proportion (mass%) of the remaining materials in the feedstock and product at a boiling point ≥ 370 °C.

[0091]

Number

[0092]

Number

[0093] where

[0094]

Number

[0095] corresponds to the proportion (mass %) of materials in the product and feedstock between the boiling points “x and y”. S x-y and Y x-y corresponds to the selectivity and yield of the hydrocarbon fraction between the boiling points “x and y”. The conversion per acid site was calculated by dividing the obtained conversion by the total number of acid sites quantified by pyridine FTIR spectroscopy at 150 °C.

[0096] Table 5 shows the acid properties and catalytic performance of the parent zeolite and the synthesized U-S-TMS. Despite having a lower concentration of zeolite-based acid sites compared to the parent zeolite, the HOCMM synthesized herein demonstrates excellent catalytic performance. Figure 8 is a plot of the hydrocracking activity (conversion percentage per acid site) and selectivity (naphtha, middle distillate, and heavy distillate) of the catalysts formed using the parent zeolite, and the synthesized HOCMM, U-S-TMS. The HOCMM synthesized herein demonstrates a higher conversion and naphtha selectivity compared to the parent zeolite.

[0097] The tuning of the associated physicochemical properties induced by achieving meso symmetry and the hexagonal symmetric mesophase led to an increased product selectivity, i.e., a higher naphtha yield.

[0098] The investigation of the properties of coke is also used to determine the catalyst stability and lifetime. In this regard, the properties of the coke with respect to the catalyst used were quantified from the CO2 profiles obtained from combustion using temperature-programmed oxidation. Figure 9 shows the CO2 profiles from coke combustion in the upper part and temperature-programmed oxidation of the spent catalyst in the lower part, where pattern (a) represents the parent zeolite and pattern (b) represents the hexagonal HOCMM of the present specification. The catalyst showed two main peaks in the regions of 320 - 500 °C and 500 - 640 °C corresponding to external coke and internal coke (zeolite micropores) present in the mesopores, respectively. Without being bound by theory, the internal coke is predicted to be the reason for zeolite deactivation due to its limited combustion during regeneration under low-pressure cracking conditions, which tend to form high internal coke, especially as a result of low H / C ratios and poor accessibility to O2. In this regard, the HOCMM of the present specification showed lower internal coke deposition (15 - 20%) compared to the parent (35%) zeolite due to its high diffusion properties. In commercial hydrocracking, the zeolite component of the catalyst is extremely important for providing flexibility in the purification unit in its mode of operation, i.e., being selective for middle distillates or naphtha, and the HOCMM of the present specification can be used to operate the purification unit under various modes of operation.

[0099] The improved naphtha selectivity indicates improved accessibility to the acid sites and seems to result in secondary cracking from middle distillate hydrocarbons to naphtha hydrocarbons. The synthesized U-S-TMS possesses a high B / L acid site ratio and a 2D-meso structure, demonstrating an excellent conversion rate of the VGO feedstock and good selectivity for naphtha.

[0100] As used herein, the term "substantially" with respect to a particular composition and / or solution and / or other parameter means at least about 50% and up to 100% of a unit or amount. As used herein, the term "significantly" with respect to a particular composition and / or solution and / or other parameter means at least about 75% and up to 100% of a unit or amount. As used herein, the term "substantially" with respect to a particular composition and / or solution and / or other parameter means at least about 90, 95, 98, or 99%, and up to 100% of a unit or amount. As used herein, the term "minor portion" with respect to a particular composition and / or solution and / or other parameter means at least about 1, 2, 4, or 10% and up to about 20, 30, 40, or 50% of a unit or amount.

[0101] It should be understood that like reference numerals in the drawings represent like elements throughout the several views, and that not all components and / or steps described and illustrated in connection with the figures are required in all embodiments or arrangements. Further, the terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the invention. The singular forms "a", "an", and "the" as used herein are to be construed to include the plural forms as well, unless the context clearly dictates otherwise. The terms "including", "comprising", "having", "containing", "involving", and variations thereof as used herein, when used, specify the presence of the features, integers, steps, operations, elements, and / or components referred to, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0102] The use of terms such as "first," "second," "third," etc. in a claim to modify elements of the claim does not, in itself, imply any priority, precedence, or order of elements of one claim over another claim, or the temporal order in which acts of a method are performed, but is simply used as a label to distinguish an element of one claim having a particular name from another element having the same name (other than common terms) for distinguishing elements of the claim.

[0103] In particular, the figures and the above embodiments do not mean that the scope of the present disclosure is limited to a single embodiment, since other realizations are possible through the exchange of some or all of the described or illustrated elements. Further, if a particular element of the present disclosure can be realized partially or fully using known components, only those portions of such known components that are necessary for understanding the present disclosure are described, and detailed descriptions of other portions of such known components are omitted so as not to obscure the present disclosure. In this specification, an embodiment showing a single component does not necessarily have to be limited to other embodiments including a plurality of the same components, and vice versa, unless otherwise explicitly stated in this specification. Further, the applicant does not intend to ascribe an uncommon or special meaning to any term in this specification or the claims, unless such is explicitly stated. Further, the present disclosure includes current and future known equivalents to the known components referred to herein by way of example.

[0104] The foregoing description of specific embodiments will, without departing from the general concepts of the present disclosure, enable others skilled in the art within the scope of their knowledge, without undue experimentation, to readily modify and / or adapt various applications of such specific embodiments, thus clearly revealing in great detail the general nature of the present disclosure. Accordingly, such applications and modifications are intended to be within the meaning and scope of the equivalents of the disclosed embodiments based on the teachings and guidance presented herein. The language or terminology of this specification is for illustrative purposes and not limiting, and thus it should be understood that the terminology or language of this specification will be interpreted by those skilled in the art in combination with the knowledge of the relevant art and in light of the teachings and guidance presented herein. The dimensions discussed or shown are drawn according to one embodiment, and it should be understood that other dimensions can be used without departing from the present disclosure.

[0105] The foregoing are provided by way of example only and should not be construed as limiting. Various modifications and changes can be made to the subject matter described herein without departing from the true spirit and scope of the invention encompassed by the present disclosure, which is defined by several of the recitations in the following claims and by the structures and functions or steps that are equivalents of these recitations, without following the exemplary embodiments and applications illustrated and described.

[0106]

Table 1

[0107]

Table 2

[0108]

Table 3

[0109]

Table 4

[0110]

Table 5

Explanation of Symbols

[0111] 10 Parent CMM 12 Oligomer CMM Unit 14 Supramolecular Template Molecule, Surfactant 16 Micelle 18 HOCMM 20 Mesopore 22 Micropore

Claims

1. A composition comprising a hierarchically ordered crystalline microporous material having a hexagonal symmetric defined long-range mesoporous order, including mesopores having walls of a crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material, wherein the long-range order is defined by the presence of secondary peaks in an X-ray diffraction (XRD) pattern and / or the presence of hexagonal symmetry observable by microscopy.

2. A composition comprising a hierarchically ordered crystalline microporous material having a hexagonal symmetric defined long-range mesoporous order, including mesopores having walls of a crystalline microporous material and a group of mesostructures between the mesopores of the crystalline microporous material, wherein at least a portion of the mesopores contains micelles of a supramolecular template shaped to induce a hexagonal symmetric mesoporous order, and the supramolecular template has one or more dimensions larger than the dimensions of the micropores of the crystalline microporous material so as to limit diffusion into the micropores of the crystalline microporous material, and the dimensions are related to the head group of the supramolecular template, the tail group of the supramolecular template, or a co-template arrangement configuration that limits diffusion into the micropores of the crystalline microporous material.

3. The composition according to claim 2, further comprising an ionic co-solute.

4. The supramolecular template is characterized by a surfactant packing parameter g in the range of about 0.4 to 0.6, g = V / a 0 l wherein, V = the total volume of the surfactant tails of the supramolecular template, a 0 = the area of the head group of the supramolecular template, and l = the length of the surfactant tails of the supramolecular template The composition according to claim 2 or 3.

5. wherein the ionic cosolute is SO 4 -2 The composition according to claim 3 or 4, comprising

6. The composition according to any one of claims 3 to 5, wherein the molar ratio of the supramolecular template to the co-solute is in the range of about 0.8 to 1.

3.

7. The composition according to any one of claims 1 to 6, wherein the hexagonal mesophase has p6m, p6mm, or P63 / mmc symmetry.

8. The composition according to any one of claims 1 to 6, wherein the hexagonal mesophase has p6mm symmetry and the secondary peaks in the XRD are present at the (11) and / or (20) reflections.

9. The composition according to any one of claims 1 to 6, wherein the hexagonal mesophase has a p6mm symmetry and the long-range order is observable by microscopy looking at an electron beam perpendicular to the mesopores along the [110] zone axis or parallel to the mesopores along the [001] zone axis.

10. The composition according to any one of claims 1 to 9, wherein the crystalline microporous material comprises a zeolite or a zeolite-type material.

11. wherein the 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, the composition according to any one of claims 1 to 9.

12. The composition according to any one of claims 1 to 9, wherein the parent crystalline microporous material is a zeolite having a FAU framework.

13. A hydrocracking catalyst comprising the hierarchical ordered crystalline microporous material according to any one of claims 10, 11, or 12, an inorganic oxide component as a binder, and an active metal component.

14. The hydrocracking catalyst according to claim 13, wherein the hierarchical ordered crystalline microporous material comprises about 0.1 to 99, 0.1 to 90, 0.1 to 80, 0.1 to 70, 0.1 to 50, 0.1 to 40, 2 to 99, 2 to 90, 2 to 80, 2 to 70, 2 to 50, 2 to 40, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 50, or 20 to 40% by mass of the hydrocracking catalyst.

15. The hydrocracking catalyst according to claim 13 or 14, 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, phosphorus-alumina-zirconia, alumina-zirconia-titania, and phosphorus-alumina-titania.

16. The hydrocracking catalyst according to claim 13 or 14, wherein the inorganic oxide component comprises alumina.

17. The hydrocracking catalyst according to claim 16, wherein the crystalline microporous material comprises FAU zeolite.

18. The hydrocracking catalyst according to claim 17, wherein the active metal component comprises one or more of Mo, W, Co, or Ni (oxide or sulfide).

19. The hydrocracking catalyst according to any one of claims 13 to 17, wherein the active metal component comprises one or more metals selected from Groups 6, 7, 8, 9, or 10 of the IUPAC Periodic Table of the Elements.

20. A process for hydrocracking a hydrocarbon oil, comprising a step of hydrocracking the hydrocarbon oil with the hydrocracking catalyst according to any one of claims 13 to 19.

21. The method according to claim 20, wherein the hydrocarbon oil comprises a recycle stream obtained from hydrocracking of VGO, straight-run VGO, or pretreated straight-run VGO, based on the selectivity to naphtha adjusted as a function of the hexagonal symmetric mesophase.

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