Zeolite beta particles having mesopores arranged radially at the center, and method for producing the same.

Abstract

Zeolite beta particles having radially arranged mesopores and a method for producing the same are disclosed herein. In one or more embodiments, the zeolite beta particles may comprise a beta-zeolite framework containing a plurality of micropores having a diameter of 2 nm or less. In embodiments, the beta-zeolite framework may include alumina and silica. In embodiments, the zeolite beta particles disclosed herein may include a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. In embodiments, the plurality of mesopores may be arranged in a central radial configuration, so that the mesopores extend from the central region of the zeolite beta particle toward the edge of the zeolite beta particle.

Description

Description of Related Applications

[0001] This application claims priority to U.S. Patent Application No. 18 / 336,625, filed on June 16, 2023, which is incorporated herein by reference in its entirety.

Technical Field

[0002] The embodiments described herein relate generally to porous materials and, more particularly, to zeolites.

Background Art

[0003] Materials with pores, such as zeolites, can be used in many petrochemical industrial applications. For example, such materials can be used as catalysts in various reactions that convert hydrocarbons and other reactants from feedstock chemicals into product chemicals. Zeolites can be characterized by a microporous framework type. Over the past few decades, various types of zeolites have been identified. The types of zeolites are generally described by the framework type, and a particular zeolite material can be more specifically identified by various names such as ZSM-5 and beta.

Summary of the Invention

[0004] Based on the above uses of zeolites, novel zeolite compositions and methods for their production have attracted attention. Embodiments of the present disclosure are directed to zeolite materials and processes for producing such materials. Specifically, the embodiments disclosed herein relate to zeolite beta particles having radially arranged mesopores. According to one or more embodiments, such beta zeolites having radially arranged mesopores can facilitate the diffusion of reactant species to the active sites present within the beta zeolite particles. Such properties can result in improved catalytic performance when used in reactions such as cracking reactions.

[0005] According to one or more embodiments disclosed herein, zeolite beta particles may comprise a beta-zeolite framework containing a plurality of micropores having a diameter of 2 nm or less. In embodiments, the beta-zeolite framework may include alumina and silica. In embodiments, the zeolite beta particles disclosed herein may have a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. In embodiments, the plurality of mesopores may be arranged in a central radial arrangement, so that the mesopores extend from the central region of the zeolite beta particle toward the edge of the zeolite beta particle.

[0006] According to one or more additional embodiments, a method for producing zeolite beta particles containing a plurality of mesopores arranged in a central radial configuration is a step of dissolving a parent zeolite in a basic solution to produce a basic zeolite solution, wherein the parent zeolite is * The process may include: a step of including micropores defined by a BEA-type microporous framework; a step of adding a supramolecular template agent and an ionic eusolute to a basic zeolite solution to form a supramolecular template agent / eusolute / zeolite mixture; a step of treating the supramolecular template agent / eusolute / zeolite mixture with hot water for a period of time to form a hot water-treated supramolecular template agent / eusolute / zeolite mixture; a step of separating a solid zeolite product from the hot water-treated supramolecular template agent / eusolute / zeolite mixture, wherein the solid zeolite product includes a plurality of mesopores arranged in a central radial configuration, and the plurality of mesopores include a supramolecular template agent; and a step of removing the supramolecular template agent from the solid zeolite product to produce zeolite beta particles containing mesopores arranged in a central radial configuration.

[0007] Both the above-mentioned general description and the following detailed description describe various embodiments and should be understood as being intended to provide an overview or framework for understanding the nature and features of the subject matter described in the claims. Additional features and advantages of the embodiments are stated in the detailed description, some of which will be readily apparent to those skilled in the art from the description, including the accompanying drawings and claims, or will be recognized by carrying out the described embodiments. The drawings are included to give a further understanding of the embodiments and, together with the detailed description, serve to illustrate the principles and operation of the subject matter described in the claims. However, the embodiments shown in the drawings are of a descriptive and illustrative nature and are not intended to limit the subject matter described in the claims. [Brief explanation of the drawing]

[0008] The following detailed description of specific embodiments of this disclosure will be best understood when read in conjunction with the following drawings, which similar structures are given the same reference numerals. [Figure 1] A flowchart illustrating the synthesis of zeolite beta particles containing multiple radially arranged mesopores according to one or more embodiments of the present disclosure. [Figure 2A] Transmission electron microscope (TEM) images of zeolite beta particles containing multiple radially arranged mesopores according to one or more embodiments of the present disclosure. [Figure 2B] TEM image of a single zeolite beta particle containing multiple radially arranged mesopores according to one or more embodiments of the present disclosure. [Figure 3] TEM image of comparative zeolite beta particles containing multiple mesopores arranged in a long-range mesopore order with cubic symmetry, although not radially arranged. [Figure 4A] TEM image of comparative zeolite beta particles that do not contain multiple mesopores. [Figure 4B] TEM image of comparative zeolite beta particles that do not contain multiple mesopores. [Figure 4C]TEM image of comparative zeolite beta particles that do not contain multiple mesopores. [Figure 5] N2 physicoadsorption isotherms of (a) zeolite beta particles (without mesopores) and (b) zeolite beta particles containing a plurality of radially arranged mesopores, according to one or more embodiments of the present disclosure. [Figure 6A] Figures showing small-angle X-ray diffraction ("XRD") patterns of (a) zeolite beta particles (without mesopores) and (b) zeolite beta particles containing multiple radially arranged mesopores, according to one or more embodiments of the present disclosure. [Figure 6B] Figure showing (a) zeolite beta particles (without mesopores) and (b) zeolite beta particles containing multiple radially arranged mesopores, according to one or more embodiments of the present disclosure. [Modes for carrying out the invention]

[0009] Herein, various embodiments will be described in more detail. Some of these embodiments are shown in the accompanying drawings. Wherever possible, the same reference numerals will be used throughout the drawings to refer to identical or similar parts.

[0010] One or more embodiments described herein relate to zeolite beta particles having multiple radially arranged mesopores. As used throughout this specification, “zeolite” or “zeolite material” generally refers to microporous inorganic materials having regularly spaced intracrystalline cavities and pathways of molecular size. The microporous structure of zeolites can be advantageous for catalytic activity by providing a large surface area and desirable size / shape selectivity. Therefore, zeolites can be used in many petrochemical applications, such as reactions that convert hydrocarbons and other reactants from raw material chemicals into product chemicals by decomposition.

[0011] In general, zeolites can be characterized by the microporous framework type that defines their microporous structure. The framework types are described, for example, in "Atlas of Zeolite Framework Types" by Christian Baerlocher et al. (Elsevier, 2007, 6th revised edition), the teachings of which are incorporated herein by reference. The zeolite particles described in one or more embodiments are: * It can have a BEA-type microporous skeleton. This is a type found in zeolite beta. * The BEA-type microporous framework has a three-dimensional network consisting of 12-membered ring pores and is characterized by an intergrowth structure of two or more polymorphs with pore diameters of 0.56 nm × 0.56 nm and 0.66 nm × 0.67 nm. In the embodiments disclosed herein, the micropores of the zeolite beta particles may have a diameter of 0.1 nm or more and 2 nm or less.

[0012] In embodiments, the zeolite beta described herein may be formed as generally spherical or irregularly spherical (i.e., non-spherical) particles. In embodiments, the particles disclosed herein have a “particle size” which can be measured as the maximum distance between two points located on a single zeolite particle. For example, the particle size of a spherical particle would be its diameter. In other shapes, the particle size can be measured as the distance between the two furthest points on the same particle, where these points may be located on the outer surface of the particle.

[0013] The particle size can be determined, for example, by visual inspection using a microscope, or by obtaining the hydrodynamic radius by dynamic light scattering ("DLS"). The particle size may be the average particle size. In embodiments, the particles disclosed herein may have an average particle size of 100 nm to 1000 nm, 150 nm to 750 nm, or 200 nm to 500 nm.

[0014] In one or more embodiments, the zeolite beta particles described herein *The BEA-type microporous framework may contain alumina and silica, which are compatible with the materials contained in zeolite beta, as will be understood by those skilled in the art. The silica-to-alumina ratio in zeolite beta can vary. According to one or more embodiments described herein, the molar ratio of silica to alumina in zeolite beta may be 10 to 10,000, for example, 10 to 5,000, 10 to 1,000, 10 to 500, 10 to 100, 10 to 80, 50 to 10,000, 50 to 5,000, 50 to 1,000, 50 to 500, or 50 to 100.

[0015] In one or more embodiments, the zeolite beta particles disclosed herein may further include a plurality of mesopores having a diameter of 2 nm or more and 50 nm or less. In embodiments, the plurality of mesopores may be arranged in a “centrally radial arrangement”. As used herein, a centrally radial arrangement of mesopores means that at least a portion of the mesopores extends from the central region of the zeolite beta particle toward the edge of the zeolite beta particle. Generally, the “central region” of the zeolite beta particle may be anywhere inside the zeolite beta particle, but may be the center or near it. As used herein, the description “radially arranged mesopores” refers to a plurality of mesopores arranged in a centrally radial arrangement. In some embodiments, a portion of the mesopores may not be oriented toward a centrally radial arrangement. However, in one or more embodiments, the majority of the volume of the mesopores, such as at least 75%, at least 90%, at least 95%, and even at least 99%, may constitute a centrally radial arrangement as described herein.

[0016] In general, as detailed in the subsequent examples section, the central radial arrangement of mesopores can be determined using microscopy, such as transmission electron microscopy (TEM). The central radial arrangement of mesopores in the disclosed zeolite beta particles can be observed by looking at the difference in electron density contrast in TEM micrographs. Figure 2B shows mesopores arranged in a central radial pattern. For comparison, Figures 3 and 4A-4C do not include mesopores arranged in a central radial pattern. Not all pores need to be strictly radial, and they generally show a central radial pattern compared to conventional zeolites. Based at least these examples, a person skilled in the art can determine the presence or absence of a central radial arrangement based on a visual inspection using a microscope.

[0017] In the embodiments of zeolites disclosed herein, radially arranged mesopores can be interconnected as a three-dimensional network by branches and sub-branching of mesopores and zeolite micropores. While not bound by any particular theory, it is thought that such a highly complex network of mesopores and micropores can facilitate the diffusion of reactant species to the active sites located within the zeolite beta particles. Furthermore, unlike conventional mesoporous zeolites in which axial mesopores open only at both ends of the zeolite particle, the radial mesopores in the zeolite beta particles described herein open to the outer surface of the zeolite particle, thereby enabling the development of novel catalytic systems and materials. While not bound by any particular theory, it is thought that such accessibility on the surface of the zeolite particle allows molecules such as asphaltenes, hydrocarbons that boil in vacuum gas oil fractions (350-565°C), and other substances present in the heavy fractions of crude oil and petrochemicals to access the mesoporous active sites.

[0018] In the embodiment, the zeolite beta particles of this application have a micropore surface area ("S") as defined by Brunauer-Emmett Teller ("BET") analysis, as will be understood by those skilled in the art. mic ) and total surface area ("S tot") can be had. In an embodiment, the zeolite beta particles of the present application are 10 square meters per gram ("m 2 / g") to 800 m 2 / g, for example, 1 m 2 / g to 100 m 2 / g, 100 m 2 / g to 250 m 2 / g, 250 m 2 / g to 500 m 2 / g, or 500 m 2 / g to 800 m 2 / g, or any combination of these ranges of S mic can be had. In an embodiment, the zeolite beta particles of the present application are 100 m 2 / g to 1800 m 2 / g, for example, 100 m 2 / g to 500 m 2 / g, 500 m 2 / g to 1000 m 2 / g, 1000 m 2 / g to 1500 m 2 / g, or 1500 m 2 / g to 1800 m 2 / g, or any combination of these ranges of S tot can be had. In an embodiment, the zeolite beta particles of the present application are at least 10% greater, at least 15% greater, at least 20% greater, or at least 25% greater than the S tot of the parent zeolite. tot can be had.

[0019] In one or more embodiments, the zeolite beta particles described herein, as will be understood by those skilled in the art, have a micropore volume ("V mic ") defined using the t-plot method, and a total pore volume ("V tot ") defined by BET analysis. In one or more embodiments, the zeolite beta particles described herein are 0.05 to 0.50 cubic centimeters per gram ("cm 3 / g"), for example, 0.05 cm 3From 0.10cm / g 3 / g, 0.10cm 3 / g to 0.20cm 3 / g, 0.20cm 3 / g to 0.30cm 3 / g, 0.30cm 3 / g to 0.40cm 3 / g, or 0.40cm 3 / g to 0.50cm 3 / g's V mic It can have the following characteristics. In this embodiment, the zeolite beta particles are 0.01 cm 3 From 1.5cm / g 3 / g, for example, 0.01cm 3 From 0.25cm / g 3 / g, 0.25cm 3 From 0.5cm / g 3 / g, 0.5cm 3 From / g to 0.75cm 3 / g, 0.75cm 3 / g to 1cm 3 / g, 1cm 3 From 1.25cm / g 3 / g, 1.25cm 3 From 1.5cm / g 3 V / g or any combination of these ranges tot It can have the following. In the embodiment, the zeolite beta particles of this application are V of the parent zeolite. tot V is at least 50% larger, at least 100% larger, at least 125% larger, at least 150% larger, at least 175% larger, or at least 200% larger. tot It can have.

[0020] The mesopore size distribution can be calculated by applying density functional theory ("DFT") to the adsorption branches of the N2 adsorption isotherm using Micromeritics' Microactive software, as will be understood by those skilled in the art. In embodiments of zeolite beta particles disclosed herein, the average mesopore size of radially arranged mesopores may range from 2 nm to 50 nm, for example, from 2.5 nm to 15 nm, 5 nm to 10 nm, or 7 nm to 8 nm. In embodiments, branches and sub-branches of mesopores interconnecting radially arranged mesopores may similarly have an average mesopore size distribution ranging from 2 nm to 50 nm, but may differ from the average mesopore size of the radially arranged mesopores. In embodiments, branches and sub-branches of mesopores interconnecting radially arranged mesopores may have an average mesopore size distribution smaller than the average mesopore size of the radially arranged mesopores.

[0021] A method for producing the zeolite beta particles described herein is also now disclosed. Zeolite beta particles can be synthesized by dissolving a “parent” zeolite beta into a plurality of oligomeric units via a base, followed by surfactant-mediated reconstruction of the oligomeric units. This dissolution and reconstruction step is controlled to minimize or avoid amorphization of the parent zeolite. The method disclosed herein produces zeolite beta particles having a plurality of radially arranged mesopores.

[0022] Figure 1 shows one route for producing the currently disclosed zeolite. However, other suitable methods may be utilized, including methods not yet discovered, for producing the currently disclosed zeolite beta particles having radially arranged mesopores as described herein. Referring here to Figure 1, the synthesis method disclosed herein may include a step of dissolving a pre-formed "parent" zeolite beta 10 in a basic solution while heating, stirring, or both, to produce a basic zeolite solution 20. In embodiments, the pre-formed zeolite is *It may contain a BEA microporous skeleton. In the embodiment, dissolving a pre-formed parental zeolite in a basic solution can result in desilicification. In the embodiment, dissolving a pre-formed parental zeolite in a basic solution can decompose the pre-formed parental zeolite into a plurality of oligomer units.

[0023] According to the method described herein, a supramolecular template agent ("STA") and an ionic eusolute can be added to a basic zeolite solution while heating, stirring, or both, to produce an STA / eusolute / zeolite mixture 30. The STA / eusolute / zeolite mixture 30 can be subjected to hot water treatment for a period of time to obtain a hot water treated mixture 40. From the hot water treated mixture 40, a solid zeolite product 50 having radially arranged mesopores can be separated and washed. If necessary, the solid zeolite product 50 may be dried at this stage. In the embodiment, the mesopores of the solid zeolite product 50 may contain STA. The STA can be removed from the solid zeolite product 50 to produce zeolite beta particles 60 having mesopores in a centrally radial arrangement.

[0024] In the embodiments, the basic zeolite solution 20 may contain a basic reagent. In the embodiments, the basic reagent may contain one or more basic compounds to maintain the basic zeolite solution 20 at a pH level higher than about 8. In the embodiments, before dissolving the parent zeolite beta 10, the concentration of the basic reagent in the basic solution may be from about 0.1 moles per liter ("M") to about 2.0 M. In certain embodiments, the basic reagent may be provided at a concentration from about 0.1 mass percent (mass%) to 5 mass%. In the embodiments, the basic reagent may contain urea, ammonium hydroxide, or alkali metal hydroxide.

[0025] In some embodiments, the rate and extent of dissolution of the parent zeolite beta 10 are controlled by using urea as an in-situ base precursor capable of generating ammonium hydroxide, which is a base. Urea may also be included in the basic solution. In such embodiments, a high concentration of urea can be used in the initial step. Urea is pH neutral under ambient conditions and can be uniformly dispersed throughout the zeolite micropores without dissolving the parent zeolite beta 10. Over time, the urea is gradually hydrolyzed to ammonium hydroxide, slowly increasing the pH of the basic zeolite solution 20 and allowing control over the dissolution of the parent zeolite beta 10.

[0026] In the embodiments of the disclosed method, the basic zeolite solution 20 can be stirred by agitation or other means for a period of time from 0.1 minutes to 60 minutes before adding STA and the ionic eusolute. In the embodiments, the basic zeolite solution 20 can be stirred at a temperature of 20°C to 80°C before adding STA and the ionic eusolute.

[0027] In the embodiment, the STA / co-solubility / zeolite mixture 30 may contain STA at a concentration of about 0.01 M to about 0.5 M. In the embodiment, the STA may contain a surfactant having a functional head group and a functional tail group. In such an embodiment, the dimensions of at least one of the functional head group or functional tail group of the surfactant may be larger than the diameter of the micropores of the parent zeolite beta 10. In the embodiment, the dimensions of at least one of the functional head group or functional tail group of the surfactant may limit the diffusion of the supramolecular template agent into the micropores of the parent zeolite beta 10.

[0028] In the embodiment, STA may contain at least one cation, such as an alkylammonium cation. In the embodiment, the cation of STA is Cl - , Br - , I - , or OH -It can be paired with anions such as [specific anions]. In the embodiment, STA may include dioctadecyldimethylammonium chloride or a derivative thereof.

[0029] In this embodiment, the ionic co-solubile is a nitrate ion (NO3) in the form of a nitrate. - ) may include. In such embodiments, the nitrate may include ammonium nitrate or a metallic nitrate, the metal of which may be an alkali metal, alkaline earth metal, transition metal, precious metal, or rare earth metal. In embodiments, the ionic co-solubile may include sodium nitrate.

[0030] According to the method described herein, the STA / co-solubide / zeolite mixture 30 can be subjected to hot water treatment for a period of 4 hours ("h") to 168 hours. In some embodiments, the STA / co-solubide / zeolite mixture 30 can be subjected to hot water treatment at a temperature of approximately 70°C to approximately 250°C. In some embodiments, the solid zeolite product 50 can be washed with water after being removed from the hot water-treated mixture 40. In some embodiments, the solid zeolite product 50 can be dried at a temperature of 100°C to 200°C for a period of 1 hour to 48 hours.

[0031] In embodiments of the method disclosed herein, the solid zeolite product 50 may include a plurality of micropores and a plurality of radially arranged mesopores, the mesopores of which include STA. According to embodiments of the method herein, STA can be removed from the mesopores of the solid zeolite product 50 to produce zeolite beta particles 60 having radially arranged mesopores.

[0032] In the embodiment, STA can be removed from the solid zeolite product 50 by various chemical or physical methods, such as calcination, solvent extraction, chemical oxidation, ionic liquid treatment, supercritical CO2 treatment, microwave-assisted treatment, ultrasonic-assisted treatment, ozone treatment, and plasma technology. In the embodiment, a preferred method for removing STA is calcination. [Examples]

[0033] Various embodiments of the described method are further illustrated by the following examples. These examples are illustrative and do not limit the subject matter of this disclosure.

[0034] Micropore surface area ("S mic "), total surface area ("S tot "), and total pore volume ("V tot The micropore volume (V) was determined using the Brunauer-Emmett-Teller ("BET") method in the P / P0 range of 0.1 to 0.3. The t-plot method was used to determine the micropore volume (V). mic ) was inferred. Nitrogen physicoadsorption measurements were performed at -196°C using an ASAP 2420 porosimeter from Micromeritics. The mesopore size distribution (D) was obtained using a DFT model applied to the adsorption branches of the N2 physicoadsorption isotherm.

[0035] X-ray diffraction (XRD) measurements were performed using a Bruker D8-Twin diffractometer equipped with a CuKα (λ=0.154 nm) detector. Data were recorded in the range of 0.5 to 50 θ / degree. The voltage and current were 40 kV and 40 mA, respectively, and the scanning speed was 0.5 degrees per minute.

[0036] Transmission electron microscopy (TEM) imaging was performed using an FEI Titan-ST transmission electron microscope with an operating voltage of 300 kV.

[0037] Example 1 - Embodiment of radial mesopores First, 1.0 g of urea was dissolved in 10.0 g of water to form a homogeneous solution. To this solution, 1.0 g of dried zeolite beta CP-811T-100 (SiO2:Al2O3 ≈ 100 (moles:moles)) was added and stirred for 0.5 hours. Then, 20 mL of water, 0.1 g of NH4NO3, and 2.0 mL of dioctadecyldimethylammonium chloride (42.0 mass%) in methanol were added sequentially. This mixture was stirred at room temperature for 2 hours. The resulting solution was subjected to hot water treatment at 170 °C for 3 days. The resulting solid was filtered, washed with water, and dried at 120 °C for 24 hours. The dried solid was calcined in air at 550 °C for 6 hours at a heating rate of 60 °C per hour to produce zeolite beta particles with mesopores arranged in a central radial configuration. Figures 2A and 2B show microscopic images of this embodiment, illustrating mesopores arranged radially from the center.

[0038] Comparative Example 2 - Embodiment of Non-Radial Mesopores First, 1.0 g of urea was dissolved in 10.0 g of water to form a homogeneous solution. 1.0 g of dried zeolite CP-814C (SiO2:Al2O3≈300) was added to this solution and stirred for 0.5 hours. Then, 20 mL of water, 0.1 g of NH4NO3, and 2.0 mL of DOAC (42.0% by mass in methanol) were added sequentially. This mixture was stirred at room temperature for 2 hours. This mixture was further stirred at room temperature for 2 hours. The resulting solution was subjected to hot water treatment at 150°C for 3 days. 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 per hour to produce zeolite beta particles with cubic arrangement of mesopores. Figure 3 shows a microscopic image of this sample, revealing a beta-zeolite with cubic symmetry but lacking radially arranged mesopores, instead possessing mesopores arranged in a long-range order.

[0039] Comparative Example 3 - Embodiment without mesopores Comparative Example 3 consists of a conventional commercially available zeolite beta (SiO2:Al2O3≈100(moles:moles)) (CP-811T, commercially available from Zeolyst) that does not have mesopores. Figures 4A-4C show microscopic images of this sample.

[0040] Example 4 - Characterization of the sample TEM images of zeolite beta particles of the present invention and comparative examples are shown in Figures 2-4. Figure 2A shows TEM images of multiple zeolite beta particles of the present invention, Example 1 ("E1"), revealing that the particles have a cuboidal morphology with a particle size ranging from 200 to 500 nm. Figure 2B shows a TEM image of a single zeolite beta particle E1 of the present invention, revealing an open mesostructure in which mesopores are organized radially from the center to the outer edge of the particle. For comparison, Figure 3 shows a TEM image of Comparative Example 2 ("CE2"), a mesoporous zeolite beta particle in which the mesopores have a long-range order with cubic symmetry rather than a central radial arrangement. Figures 4A-4C show TEM images of Comparative Example 3 ("CE3"), which does not contain any mesopores.

[0041] The TEM data for E1 shows that radial mesopores are interconnected by branches and sub-branches of mesopores and zeolite micropores, forming a three-dimensional hierarchical network. The radially arranged mesopores have a wide range of dimensions from 3 to 15 nm, while the interconnected branches of mesopores and micropores are relatively small. The inset in Figure 4B shows the lattice pattern corresponding to the BEA type.

[0042] Table 1 summarizes the structural properties and texture characteristics of E1 and CE3.

[0043] [Table 1]

[0044] The data in Table 1 shows that the zeolite beta particles of the present invention disclosed herein are compared to conventional zeolite beta particles (CE3, 623m).2 Total surface area (714 m² for E1) higher than the total surface area ( / g) 2 This indicates that it has ( / g). The zeolite beta particles of the present invention have the same properties as conventional zeolite beta particles (0.25 cm for CE3). 3 Total pore volume (for E1) higher than ( / g) is 0.54 cm³. 3 It also has ( / g). Since both the microporous surface area and microporous volume of E1 are close to or smaller than those of CE3, the increase in total surface area and total pore volume is due to the presence of mesopores in the zeolite beta particles of the present invention.

[0045] Figure 5 shows the N2 physicoadsorption isotherms for E1(b) and CE3(a). Evaluation of the adsorption and desorption branches of these adsorption isotherms, and the hysteresis between them, indicates that the mesoporous zeolite beta exhibits a type IV adsorption isotherm with broad hysteresis ranging from 0.45 to 0.9 P / P0, suggesting the presence of mesopores of varying sizes. The broad pore size distribution obtained from DFT also supports the presence of mesopores. Furthermore, the high N2 adsorption amount with a P / P0 of less than 0.1 suggests that the prepared structure also possesses a significant amount of microstructure. In contrast, CE3 generates a type I adsorption isotherm, indicating a microstructure without mesopores.

[0046] Figures 6A and 6B show the small-angle (6A) and large-angle (6B) XRD patterns for E1(b), a zeolite beta particle of the present invention, and commercially available CE(a). In contrast to CE3, the XRD pattern of zeolite E1 of the present invention shows broad reflection in the low-angle region, suggesting that the mesopores are uniformly organized without any particular order within the crystalline region. The large-angle XRD pattern of the mesoporous zeolite beta is similar to that of the parent zeolite beta, lacking amorphous phases and impurities, suggesting that the zeolite structure is maintained even in the post-synthesis modification process.

[0047] This disclosure includes one or more limited aspects.

[0048] The first embodiment includes a zeolite beta particle comprising a beta zeolite skeleton containing a plurality of micropores having a diameter of 2 nm or less, the beta zeolite skeleton containing alumina and silica, and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm, arranged in a central radial configuration, and thus comprising a plurality of mesopores extending from the central region of the zeolite beta particle toward the edge of the zeolite beta particle.

[0049] The second aspect is that the total surface area of ​​the zeolite beta particles is 500 m 2 / g to 1500m 2 This includes any of the above embodiments, where / g is the same.

[0050] A third aspect is that the micropore surface area of ​​the zeolite beta particles is 250 m². 2 / g to 750m 2 This includes any of the above embodiments or combinations thereof, where / g.

[0051] A fourth aspect is that the micropore volume of the zeolite beta particles is 0.10 cm². 3 From 0.25cm / g 3 This includes any of the above embodiments or combinations thereof, where / g.

[0052] A fifth aspect is a zeolite beta particle with a total pore volume of 0.25 cm³. 3 From 1.0cm / g 3 This includes any of the above embodiments or combinations thereof, where / g.

[0053] The sixth embodiment includes any of the above embodiments or a combination thereof, wherein the molar ratio of silica to alumina is from 10 to 500.

[0054] A seventh aspect is a method for converting a chemical substance, comprising the step of contacting a reactant with zeolite beta particles of any of the above aspects.

[0055] The eighth aspect includes the seventh aspect, wherein the reactant is a hydrocarbon.

[0056] The ninth aspect is a method for producing zeolite beta particles containing a plurality of mesopores arranged in a central radial configuration, comprising the step of dissolving a parent zeolite in a basic solution to produce a basic zeolite solution, wherein the parent zeolite is * The method includes the steps of: including micropores defined by a BEA-type microporous framework; adding a supramolecular template agent and an ionic eusolute to the basic zeolite solution to form a supramolecular template agent / eusolute / zeolite mixture; treating the supramolecular template agent / eusolute / zeolite mixture with hot water for a period of time to form a hot water-treated supramolecular template agent / eusolute / zeolite mixture; separating a solid zeolite product from the hot water-treated supramolecular template agent / eusolute / zeolite mixture, wherein the solid zeolite product comprises a plurality of mesopores arranged in a central radial configuration, and the plurality of mesopores contain the supramolecular template agent; and removing the supramolecular template agent from the solid zeolite product to produce zeolite beta particles containing mesopores arranged in a central radial configuration.

[0057] A tenth embodiment includes a ninth embodiment, further comprising a step of washing the solid zeolite product after a step of separating the solid zeolite product from the hydrothermal supramolecular template agent / co-solute / zeolite mixture.

[0058] An eleventh embodiment includes a tenth embodiment, further comprising a step of drying the solid zeolite product before the step of removing the supramolecular template agent.

[0059] The twelfth embodiment includes the ninth embodiment, wherein the step of removing the supramolecular template agent includes a step of calcining the solid zeolite product.

[0060] The 13th embodiment includes any one or any combination of the 9th to 11th embodiments, wherein the basic solution contains urea.

[0061] A 14th embodiment includes any one or any combination of the 9th to 12th embodiments, wherein the supramolecular template agent comprises a surfactant having a functionalized head group and a functionalized tail group, wherein the dimensions of at least one of the functionalized head group or the functionalized tail group are greater than the diameter of the micropores of the zeolite, and the dimensions of at least one of the functionalized head group or the functionalized tail group restrict the diffusion of the supramolecular template agent into the micropores of the zeolite.

[0062] The 15th aspect includes any one or any combination of the 9th to 13th aspects, wherein the supramolecular template agent comprises dioctadecyldimethylammonium chloride.

[0063] The sixteenth embodiment includes any one or any combination of the ninth to fifteenth embodiments, wherein the ionic co-solubile contains a nitrate and the metal is an alkali metal, alkaline earth metal, transition metal, precious metal, or rare earth metal.

[0064] The 17th aspect is the S of the zeolite beta particles. tot is the S of the parent zeolite tot Includes any one or any combination of the 9th to 16th embodiments, which is at least 10% greater.

[0065] The 18th aspect is the V of the zeolite beta particles. tot V of the parent zeolite tot Including one or any combination of the 9th to 17th embodiments, which is at least 50% greater.

[0066] While the subject matter of this disclosure has been described in detail with reference to specific embodiments, it should be noted that the various details described herein should not be interpreted as suggesting that these details relate to essential components of the various embodiments described herein, even if certain elements are shown in the drawings accompanying this specification. Rather, the appended claims should be interpreted as representing the sole scope of this disclosure and the corresponding scope of the various embodiments described herein. Furthermore, it will be evident that modifications and alterations are possible without departing from the scope of the appended claims.

Claims

1. In zeolite beta particles, A beta-zeolite skeleton containing multiple micropores having a diameter of 2 nm or less, and a beta-zeolite skeleton containing alumina and silica, A plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm, arranged in a central radial configuration, and thus a plurality of mesopores extending from the central region of the zeolite beta particle toward the edge of the zeolite beta particle, Zeolite beta particles equipped with these properties.

2. The total surface area of ​​the zeolite beta particles is 500 m². ２ / g to 1500m ２ Zeolite beta particles according to claim 1, wherein the particle size is / g.

3. The micropore surface area of ​​the zeolite beta particles is 250 m². ２ / g to 750m ２ Zeolite beta particles according to claim 1 or 2, wherein the particle size is / g.

4. The micropore volume of the zeolite beta particles is 0.10 cm². ３ / g to 0.25cm ３ / g is The total pore volume of the zeolite beta particles is 0.25 cm³. ３ / g to 1.0cm ３ / g is, or The molar ratio of silica to alumina is between 10 and 500. A method according to any one of claims 1 to 3, wherein one or more of the above conditions are met.

5. A method for converting a chemical substance, comprising the step of contacting a reactant with zeolite beta particles according to any one of claims 1 to 4, wherein the reactant is a hydrocarbon.

6. In a method for producing zeolite beta particles containing multiple mesopores arranged in a central radial configuration, A step of dissolving a parent zeolite in a basic solution to produce a basic zeolite solution, wherein the parent zeolite ＊ includes micropores defined by a BEA-type microporous framework, A step of adding a supramolecular template agent and an ionic co-solute to the basic zeolite solution to form a supramolecular template agent / co-solute / zeolite mixture. A step of treating the supramolecular template agent / co-solute / zeolite mixture with hot water over a certain period of time to form a hot water-treated supramolecular template agent / co-solute / zeolite mixture, A step of separating a solid zeolite product from the hydrothermal treated supramolecular template agent / co-solute / zeolite mixture, wherein the solid zeolite product comprises a plurality of mesopores arranged in a central radial configuration, and the plurality of mesopores contain the supramolecular template agent, and A step of removing the supramolecular template agent from the solid zeolite product to produce zeolite beta particles containing mesopores arranged in a central radial configuration, A method that includes this.

7. The method according to claim 6, further comprising the step of washing the solid zeolite product after the step of separating the solid zeolite product from the hydrothermal treated supramolecular template agent / co-solute / zeolite mixture.

8. The method according to claim 6 or 7, further comprising the step of drying the solid zeolite product before the step of removing the supramolecular template agent.

9. The method according to any one of claims 6 to 8, wherein the step of removing the supramolecular template agent includes a step of calcining the solid zeolite product.

10. The method according to any one of claims 6 to 9, wherein the basic solution comprises ammonium hydroxide formed from urea.

11. The supramolecular template agent comprises a surfactant having a functionalized head group and a functionalized tail group, The dimensions of at least one of the functionalized head group or the functionalized tail group are greater than the diameter of the micropores of the zeolite. The method according to any one of claims 6 to 10, wherein the dimensions of at least one of the functionalized head group or the functionalized tail group restrict the diffusion of the supramolecular template agent into the micropores of the zeolite.

12. The method according to any one of claims 6 to 11, wherein the supramolecular template agent comprises dioctadecyldimethylammonium chloride.

13. The method according to any one of claims 6 to 12, wherein the ionic co-solubile contains a nitrate, and the metal is an alkali metal, alkaline earth metal, transition metal, precious metal, or rare earth metal.

14. The S of the zeolite beta particles ｔｏｔ is the S of the parent zeolite ｔｏｔ The method according to any one of claims 6 to 13, which is at least 10% greater.

15. The V of the zeolite beta particles ｔｏｔ V of the parent zeolite ｔｏｔ The method according to any one of claims 6 to 14, which is at least 50% greater.

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