EMM-74 Molecular Sieve Composition, Synthesis and Use thereof

Abstract

A molecular sieve named EMM-74, characterized by a unique powder XRD pattern, its manufacturing method, and its applications.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority and benefit of U.S. Provisional Application No. 63 / 488912, filed on 7 March 2023, which is incorporated herein by reference in its entirety.

[0002] This invention relates to molecular sieve compositions, methods for producing the same, and uses thereof. [Background technology]

[0003] Natural and synthetic molecular sieve materials can be used as adsorbents and may possess catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AlPO, and mesoporous materials, are ordered porous crystalline materials with a distinct crystalline structure, as determined by X-ray diffraction (XRD). Certain molecular sieves are regularly arranged and exhibit specific X-ray diffraction patterns. Within certain molecular sieve materials, numerous cavities exist, which may be interconnected by numerous channels or pores. The size of these cavities or pores is uniform within a particular molecular sieve material. Because the dimensions of these pores are designed to accept molecules of a specific size for adsorption and reject larger molecules, these materials have become known as "molecular sieves" and are utilized in various industrial processes, such as decomposition, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0004] Molecular sieves used for catalysis and adsorption include both naturally occurring and synthesized crystalline molecular sieves. Examples of these molecular sieves include extra-large pore zeolites, large pore zeolites, medium pore zeolites, and small pore zeolites. These zeolites and their isotypes are classified by the Structural Committee of the International Zeolite Association in accordance with the rules of the IUPAC Zeolite Nomenclature Committee. According to this classification, framework-type zeolites and other crystalline microporous molecular sieves with established structures are assigned a three-letter code and are described in the "Atlas of Zeolite Framework Types," eds. Ch. Baerlocher, LB McCusker, and DH Olson, ElseVIer, Sixth Edition, 2007. These zeolites and their isotypes are also listed at http: / / america.iza-structure.org / IZA-SC / ftc_table.php.

[0005] The idealized inorganic framework structure of zeolites is a silicate framework in which all tetrahedral atoms are linked to four next-nearest tetrahedral atoms by oxygen atoms. The term “silicate,” as used herein, refers to a material containing at least silicon and oxygen atoms that are alternately bonded to one another (i.e., -O-Si-O-Si-), and optionally other atoms in an inorganic framework structure, including atoms such as boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc). Atoms other than silicon and oxygen in a framework silicate occupy some of the lattice sites occupied by silicon atoms in a “total silica” framework silicate. Therefore, as used herein, the term “framework silicate” refers to an atomic lattice containing any of the following: silicates, borosilicates, gallosilicates, ferricilicates, aluminosilicates, titanosilicates, gincosilicates, vanadosilicates, etc.

[0006] The structure of the framework silicate within a given zeolite determines the size of the pores or channels present within it. The size of these pores or channels can determine the types of processes to which the given zeolite can be applied. Currently, over 200 unique zeolite framework silicate structures are known and recognized by the Structural Committee of the International Zeolite Association, which defines a variety of pore shapes and orientations.

[0007] Framework silicates of zeolites or molecular sieves are generally characterized in terms of their ring size, where ring size refers to the number of silicon atoms (or alternative atoms as listed above) tetrahedral-coordinated with oxygen atoms in loops to define pores or channels within the zeolite. For example, an "8-ring" zeolite refers to a zeolite having pores or channels defined by eight alternately arranged tetrahedral atoms and eight oxygen atoms in loops. The pores or channels defined within a given zeolite may be symmetrical or asymmetrical, depending on the various structural constraints present in a particular framework silicate.

[0008] Zeolites can be classified into small, medium, large, and extra-large pore structures based on pore windows demarcated by 8, 10, 12, and 12 or more T atoms, respectively. Extra-large pore zeolites (greater than 12R) include, for example, AET (14R, e.g., ALPO-8), SFN (14R, e.g., SSZ-59), VFI (18R, e.g., VPI-5), CLO (20R, cloverite), and ITV (30R, ITQ-37) framework zeolites. Ultra-large pore zeolites generally have free pore diameters greater than approximately 0.8 nm. Examples of large pore zeolites (12R) include, for example, LTL, MAZ, FAU, EMT, OFF, *Examples of BEA, MOR, and SFE framework-type zeolites include mazite, ofretite, zeolite L, zeolite Y, zeolite X, ω, ZSM-2, zeolite T, beta, and SSZ-48. Large-pore zeolites generally have a free pore diameter of 0.6 to 0.8 nm. Medium (or intermediate) pore-type zeolites (10R) include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework-type zeolites, such as ZSM-5, ZSM-11, ZSM-22, MCM-22, silicilite-1, and silicilite-2. Medium-pore-type zeolites generally have a free pore diameter of 0.45 to 0.6 nm. Small-pore zeolites (8R) include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework zeolites, ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, Zeolite A, Chabazite, and ALPO-17. Small-pore zeolites generally have a free pore size of 0.3 to 0.45 nm.

[0009] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthetic mixture containing not only silica but also alumina and other sources of all elements present in molecular sieves (or zeolites). Often, structural indicators (SDAs) are also present. Structural indicators are compounds thought to promote molecular sieve formation, acting as templates for the formation of specific molecular sieve structures, thereby facilitating the formation of the desired molecular sieve. Various compounds, including various types of quaternary ammonium cations, have been used as structural indicators. Typically, the molecular sieve (or zeolite) crystals form around the structural indicator, and once crystallization is complete, the structural indicator occupies the pores of the molecular sieve. Therefore, since "as-synthesized" molecular sieves contain structural indicators within their pores, after crystallization, "as-synthesized" (or "as-manufactured") molecular sieves are usually subjected to processing steps, such as calcination, to remove the structural indicators.

[0010] For example, U.S. Patent No. 6,080,382 and Lee et al. (2002) "Organocations in Zeolite Synthesis: Fused Bicyclo [Im0] Cations and the Discovery of Zeolite SSZ-48," J. Am. Chem. Soc., v.124, pp. 7024-7034 disclose the preparation of molecular sieve SSZ-48 using decahydroquinolinium cations as structural indicators, and Y. Luo et al. (2018) "A Facile and Green Method for the Synthesis of SFE Borosilicate Zeolite and Its Heteroatom-Substituted Analogues with Promising Catalytic Performances," Chem. Eur. Jrnl., v.24(2), pp. 306-311 disclose the use of 4-dimethylaminopyridine. SSZ-48 was identified as an SFE-type zeolite containing a one-dimensional 12-membered ring (12MR) channel system with an elliptical opening (0.54 × 0.76 nm). SSZ-48 typically crystallizes in the form of fibrous rods with crystal dimensions of 0.05–0.25 × 10 microns or needles with a uniform size of approximately 0.05 × 1 micron. See also P. Wagner et al. (1999) "Electron Diffraction Structure Solution of a Nanocrystalline Zeolite at Atomic Resolution," J. Phys. Chem. B, v.103(39), pp 8245–8250.

[0011] While many different molecular sieves have been discovered, there is a continuing need for novel molecular sieves (or zeolites) with desirable properties for gas separation and drying, organic conversion reactions, and other applications. Novel molecular sieves may contain novel internal pore structures, which can increase selectivity in these processes. It is also important to identify novel structural indicators and more efficient methods for synthesizing molecular sieves in order to facilitate the production of new molecular sieves and / or reduce the production costs of known molecular sieves. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] U.S. Patent No. 6,080,382 [Non-patent literature]

[0013] [Non-Patent Document 1] Lee et al. (2002) "Organocations in Zeolite Synthesis: Fused Bicyclo [Im0] Cations and the Discovery of Zeolite SSZ-48," J. Am. Chem. Soc., v.124, pp. 7024-7034 [Non-Patent Document 2] Y. Luo et al. (2018) "A Facile and Green Method for the Synthesis of SFE Borosilicate Zeolite and Its Heteroatom-Substituted Analogues with Promising Catalytic Performances," Chem. Eur. Jrnl., v.24(2), pp. 306-311 [Non-Patent Document 3] P. Wagner et al. (1999) "Electron Diffraction Structure Solution of a Nanocrystalline Zeolite at Atomic Resolution," J. Phys. Chem. B, v.103(39), pp 8245-8250

Summary of the Invention

[0014] The present disclosure relates to molecular sieves, methods for their production, and their use.

[0015] In a first aspect, the present disclosure relates to a molecular sieve having an X-ray diffraction pattern comprising peaks at 2θ [°] as shown in Table 1 below: in its calcined form (e.g., at least a portion of the SDA has been removed), JPEG2026509429000002.jpg8693.

[0016] In a second aspect, the present disclosure relates to a molecular sieve having an X-ray diffraction pattern comprising peaks at 2θ [°] as shown in Table 2: in its as-synthesized form (e.g., the SDA has not been removed), JPEG2026509429000003.jpg9089.

[0017] In a third aspect, the present disclosure relates to a method for producing a molecular sieve, particularly a molecular sieve according to the first and / or second aspects, the following steps: (a) A step of preparing a synthetic mixture comprising water, a source of tetravalent element oxides (Y), optionally a source of trivalent element oxides (X), a structural indicator (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F), and optionally a source of alkali metal elements and / or alkaline earth metal elements (M), wherein the structural indicator (Q) is 1-methylimidazo[1,2-a]pyridine-1-a of formula I A step comprising at least one cation selected from the following: 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III, 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV, and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium of formula V: JPEG2026509429000004.jpg136132 (b) Heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve; (c) A step of recovering at least a portion of the molecular sieve from step (b); and (d) Optionally, process the molecular sieves recovered in step (c) to remove at least a portion of the structural indicator (Q). Includes.

[0018] In a fourth aspect, the Disclosure relates to a method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with a molecular sieve according to a first or second aspect of the Disclosure, or producing it according to a method of a third aspect of the Disclosure.

[0019] These and other features and attributes of this disclosure, as well as their advantageous uses and / or applications, will become apparent from the following detailed description. Of course, it will be understood that features described in relation to one aspect of the invention may be incorporated into other aspects of the invention. In particular, any two or more features described in this specification, including this abstract, may be combined to form combinations of features not specifically described herein. [Brief explanation of the drawing]

[0020] [Figure 1] The powder XRD pattern of the as-synthesized product from Example 2 is shown. [Figure 2] The powder XRD pattern of the calcined product from Example 2 is shown. [Figure 3] The SEM image of the as-synthesized product from Example 2 is shown. [Figure 4] The SEM image of the as-synthesized product from Example 7 is shown. [Figure 5] The SEM image of the as-synthesized product from Example 14 is shown. [Figure 6] The powder XRD pattern of the as-synthesized product from Example 17 is shown. [Figure 7] The powder XRD of the calcined product from Example 17 is shown. [Figure 8] The SEM image of the as-synthesized product from Example 17 is shown. [Modes for carrying out the invention]

[0021] This disclosure relates to molecular sieve compositions, methods for producing the same, and uses thereof. The molecular sieve may be referred to as EMM-74 molecular sieve, EMM-74 zeolite, or EMM-74 material.

[0022] In a first embodiment, the present disclosure relates to a firing configuration (for example, in which at least a portion of the SDA is removed by heat treatment or other treatment), as shown in Table 1 below: This relates to a molecular sieve having an X-ray diffraction pattern that includes the peak shown in JPEG2026509429000005.jpg8693.

[0023] In a further embodiment, the molecular sieve, in its firing form, is as follows (Table 1A): The X-ray diffraction pattern has a peak shown in JPEG2026509429000006.jpg87115, where the d-spacing value has a deviation determined based on the corresponding deviation ±0.20°(2θ) when converted to the corresponding d-spacing value using Bragg's law.

[0024] For example, the molecular sieves, in their firing form, are classified as follows: Table 1B (aluminosilicate) and Table 1C (borosilicate): JPEG2026509429000007.jpg91122 The aluminosilicate molecular sieve or borosilicate molecular sieve may have an X-ray diffraction pattern including the peak shown in JPEG2026509429000008.jpg91117, where the d-spacing value has a deviation determined based on the corresponding deviation ±0.20°(2θ) when converted to the corresponding d-spacing value using Bragg's law.

[0025] The XRD patterns having XRD peaks described herein use Cu(Kα) radiation.

[0026] In one or more further embodiments, the molecular sieve may have a micropore volume of 0.05 to 0.25 cc / g, for example 0.07 to 0.2, for example 0.12 cc / g, in its calcined form.

[0027] In one or more further embodiments, the molecular sieve is fired in a manner of 100-700 m 2 / g, for example 200-500m 2 / g, for example 302m2 Micropore surface area per g, and / or 5-200 m² 2 / g, for example, 10-100m 2 / g, for example 53m 2 It may have an external surface area of ​​ / g.

[0028] In one or more further embodiments, the molecular sieve is optionally, in its firing form, a material of the following formula V: (m)X2O3:YO2 (formula V), (In the formula, 0 ≤ m ≤ 0.1, X is a trivalent element, and Y is a tetravalent element. Y may contain one or more of Si, Ti, Zr, Sn, and Ge.) It may be represented by the molecular formula. For example, Y may contain Si and / or Ge, or be Si and / or Ge, for example, Y may contain Si or Si. X may contain one or more of Al, B, Fe, and Ga. In particular, X may contain Al and / or B, or be Al and / or B, for example, X may contain Al or be Al. In embodiments where Y is Si and X is Al, the molecular sieve is an aluminosilicate. In embodiments where Y is Si and X is B, the molecular sieve is a borosilicate. In embodiments where Y is Si and X is a mixture of Al and B, the molecular sieve is an aluminoborosilicate. The oxygen atom in formula V may be substituted with a carbon atom (e.g., in the form of CH2), which may come from a source of components used to produce the as-produced molecular sieve. The oxygen atom in formula V may also be substituted with a nitrogen atom, for example, after SDA has been removed. Formula V, in its calcined form, can represent a typical molecular sieve framework as defined herein, and does not mean that it is the only representation of such molecular sieve. The molecular sieve, in its calcined form, may contain SDA and / or impurities after appropriate treatment to remove SDA and impurities not considered in Formula V. Furthermore, Formula V does not include protons and charge compensation ions that may be present in the calcined molecular sieve.

[0029] The variable m represents the molar ratio relationship between X2O3 and YO2 in equation V. For example, when m is 0.025, the molar ratio of YO2 to X2O3 is 40, and the molar ratio of Y to X is 20 (for example, the molar ratio of Si / Al is 20). m may vary from 0 to 0.1, for example, at least 0.0017, or at least 0.005, or at least 0.007, or at least 0.01 to at most 0.1, or at most 0.07, or at most 0.05, for example, from 0.001 or 0.005 to 0.05 or 0.025. The molar ratio of Y to X may range from 5 to infinity (corresponding to the silicate product), for example, at least 5, or at least 7, or at least 10, or at least 15, and up to infinity, or 300 or less, or 100 or less, or 75 or less, or 50 or less, for example, 10, or 15, or 20 to infinity, or 300, or 100, or 75.

[0030] In a second embodiment, the present disclosure relates to molecular sieves, particularly molecular sieves as defined in the first embodiment, in their as-synthesized form (e.g., with SDA not removed), as shown in Table 2 below: Regarding molecular sieves having an X-ray diffraction pattern including a peak at 2θ[°] as shown in JPEG2026509429000009.jpg9391.

[0031] In a further embodiment, the molecular sieve is in its as-synthesized form as shown in Table 2A below: The X-ray diffraction pattern may include the peak shown in JPEG2026509429000010.jpg83106, where the d-spacing value has a deviation determined based on the corresponding deviation ±0.20°(2θ) when converted to the corresponding d-spacing value using Bragg's law.

[0032] For example, the molecular sieves, in their as-synthesized form, are as follows: Table 2B (aluminosilicate) and Table 2C (borosilicate): JPEG2026509429000011.jpg86116 An aluminosilicate molecular sieve or borosilicate molecular sieve having an X-ray diffraction pattern including the peaks shown in JPEG2026509429000012.jpg87114, wherein the d-spacing values have a deviation determined based on the corresponding deviation of ±0.20°(2θ) when converted to the corresponding value of d-spacing using Bragg's law.

[0033] The XRD pattern having the XRD peaks described herein uses Cu(Kα) radiation.

[0034] In one or more further embodiments, the molecular sieve, in as-synthesized form, optionally, has the following formula VI: (q)Q:(m)X2O3:YO2 (Formula VI), (where 0 < q ≦ 0.7, 0 ≦ m ≦ 0.1, and Q includes at least one cation selected from the 1-methylimidazo[1,2-a]pyridin-1-ium cation of Formula I, the 1,2-dimethylimidazo[1,2-a]pyridin-1-ium cation of Formula II, the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridin-5-ium cation of Formula III, the 1,6-dimethylimidazo[1,2-a]pyridin-1-ium cation of Formula IV, and the 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridin-4-ium of Formula V: JPEG2026509429000013.jpg132133 X is a trivalent element as defined for Formula V, and Y is a tetravalent element as defined for Formula V.) Formula VI may be represented by the molecular formula. Formula VI can represent a typical molecular sieve framework as defined herein in its as-synthesized form and therefore includes a structural indicator (Q), and does not mean that it is the only representation of such a material. The molecular sieve may contain impurities not described in Formula VI in its as-synthesized form. Furthermore, Formula VI does not include protons and charge compensation ions that may be present in the as-synthesized molecular sieve.

[0035] The variable m represents the molar ratio relationship between X2O3 and YO2 in equation VI. The value of the variable m in equation VI is the same as that described herein for equation V.

[0036] The variable q represents the molar ratio relationship between Q and YO2 in equation VI. For example, if q is 0.1, the molar ratio of Q to YO2 is 0.1. The molar ratio of Q to YO2 can be greater than 0 and less than or equal to 0.7, for example, between 0.1 and 0.6, or between 0.1 and 0.5.

[0037] In further embodiments, the framework structure of the molecular sieve of the first and / or second aspects of the present disclosure (whether in as-synthesized or calcined form) may be specified as an SFE framework type. In particular, the framework structure of the molecular sieve of the present disclosure may be specified as having a 12-membered ring-pore channel (12MR) having dimensions of 5.4 ± 0.20 Å × 7.6 ± 0.20 Å.

[0038] In yet another embodiment, at least a portion of the molecular sieve crystals of the present disclosure (whether in their as-synthesized or calcined form) may have a rod-like morphology. “At least a portion” of the molecular sieve crystals may have a rod-like morphology means that at least about 50%, e.g., at least 60%, at least 75%, or at least 85% of the molecular sieve crystals may have a rod-like morphology. “Rod-like morphology” means a crystal that is substantially in the form of elongated particles, like a rod or cylinder, and in particular has one long dimension along the c-axis (i.e., the longest dimension) and one short dimension perpendicular to the long dimension (i.e., the smallest dimension perpendicular to the long dimension and measured at the center of the long dimension), where the long dimension may be called the length (l) of the crystal and the short dimension may be called the width, thickness, or diameter (d) of the crystal. The morphology and the percentage (as volume %) of crystals having such morphology can be determined, for example, by image analysis of scanning electron microscope (SEM) micrographs using ImageJ software.

[0039] The rod-shaped molecular sieve crystals according to this disclosure typically have a length (l) of 30 nm to 10 microns (μm), particularly at least 50 nm, or at least 75 nm, or at least 100 nm, and at most 5 μm, or at most 1 μm, or at most 600 nm, e.g., at least 100 nm, or 150 nm, or 200 nm, and at most 1 μm, or at most 500 nm, or 400 nm, e.g., about 300 nm, 200 nm, or 100 nm; and a width, thickness, or diameter (d) of 20 nm to 200 nm, particularly at least 25 nm, or at least 30 nm, or at least 40 nm, and at most 100 nm, or at most 75 nm, or at most 60 nm, e.g., at least 30 nm, or 40 nm, or 45 nm, and at most 100 nm, or at most 75 nm, or 60 nm, e.g., about 30 nm to 50 nm. Molecular sieve crystals having a rod-like morphology according to this disclosure may typically have an aspect ratio, defined as the ratio of length to diameter (l / d) of the crystal, ranging from 1 to 10, particularly greater than 1, or at least 2, or at least 3, to less than 10, or at most 9, or at most 8, for example 2 to 9, or 3 to 8, or 2 to 5, or 4 to 7, for example about 2, 3, 4, 5, or 6.

[0040] In another further embodiment, at least a portion of the molecular sieve crystals of the present disclosure (whether in their as-synthesized or calcined form) may have a plate-like (or lattice-like) form. “At least a portion” of the molecular sieve crystals may have a plate-like form means that at least about 50%, e.g., at least 60%, at least 75%, or at least 85% of the molecular sieve crystals may have a plate-like form. “Plate-like form” means a substantially plate-like crystal, e.g., a disc-shaped or rectangular plate-shaped crystal, having first and second primary dimensions which can be called the length (l) and width (b) of the plate-like body (i.e., the longest dimension of the largest face of the plate-like body, and the dimension of the largest face measured at the center of the longest dimension and perpendicular to the longest dimension), and a smaller third dimension called the thickness (t) of the plate-like body (i.e., the smallest dimension perpendicular to the largest face and measured at the center of the longest dimension). The morphology and the proportion (as volume %) of crystals having the said morphology can be determined, for example, by image analysis of scanning electron microscope (SEM) images using ImageJ software.

[0041] The molecular sieve crystals having a plate-like morphology according to this disclosure may have a length / width ratio (l / b) of 1 to 5, e.g., 1 to 4, or 1 to 3, e.g., about 1, 1.5, or 2; and a length / thickness ratio (l / t) greater than 1 to 10, e.g., 2 to 8, or 3 to 6, e.g., about 4, or 5. In a more specific embodiment, the molecular sieve crystal having a plate-like form according to the present disclosure may have a length (l) of 75 nm to 1 μm, for example, at least 100 nm and at most 500 nm, or at most 300 nm, or at most 200 nm, for example, about 100 nm or 150 nm; and a thickness (t) of 5 nm to 60 nm, for example, 10 nm or 15 nm to 40 nm or 50 nm, for example, about 20 nm or 30 nm. For example, the molecular sieve crystal may have a length (l) of about 100 to 200 nm, a width (b) of about 50 to 150 nm, and a thickness (t) of about 20 to 30 nm.

[0042] Rod- and plate-like morphologies are particularly advantageous in catalytic and adsorption applications compared to fibrous (or fibrous) morphologies, which typically have an aspect ratio (l / d) greater than 10. In fact, the diffusion rate through the longest dimension of zeolite crystals is faster in such rod- and plate-like particles due to their shorter diffusion length compared to fibrous (or fibrous) particles, which have a much longer diffusion length. Furthermore, fibrous crystals have raised concerns regarding the health effects of long-term inhalation.

[0043] Accordingly, in a further embodiment, the present disclosure relates to an SFE framework type molecular sieve characterized by a rod-like or plate-like form, and in particular a plate-like form.

[0044] In a third aspect, the Disclosure relates to a method for producing molecular sieves, particularly molecular sieves as defined in the first and / or second aspects of the Disclosure, the following steps: (a) A step of preparing a synthetic mixture comprising water, a source of tetravalent element oxide (Y), optionally a source of trivalent element oxide (X), a structural indicator (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F), and optionally a source of alkali metal elements and / or alkaline earth metal elements (M), wherein the structural indicator (Q) is 1-methylimidazo[1,2-a]pyridine-1-a of formula I The cation comprises at least one cation selected from the following: 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III, 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV, and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium of formula V: JPEG2026509429000014.jpg134127 (b) A step of heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve. (c) A step of recovering at least a portion of the molecular sieve from step (b), and (d) Optionally, process the molecular sieves recovered in step (c) to remove at least a portion of the structural indicator (Q). Includes.

[0045] The structural indicator (Q) may be selected from the group consisting of the cations of formulas I, II, and / or III described above, in particular the 1-methylimidazo[1,2-a]pyridine-1-ium cation of formula I, the 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III, the 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV, or the 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium cation of formula V. The structural indicator (Q) may exist in any preferred form, for example, as a halogen such as a fluoride, chloride, iodide, or bromide, as a hydroxide, or as a nitrate, for example, in the form of its hydroxide. The structural indicator (Q) may be present in the synthetic mixture in a Q / Y molar ratio of 0.01 to 1.0, e.g., 0.05 to 1.0, or at least 0.1, or at least 0.15, and at most 0.8, or at most 0.7, or at most 0.6, e.g., 0.1 or 0.15 to 0.7 or 0.6, e.g., 0.15 to 0.5. While we do not wish to be constrained by theory, structural indicators (Q) comprising at least one cation selected from the 1-methylimidazo[1,2-a]pyridine-1-ium cation of formula I, the 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, and the 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV tend to facilitate the synthesis of molecular sieve crystals of the present disclosure having a rod-like morphology, while structural indicators (Q) comprising at least one cation selected from the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III tend to facilitate the synthesis of molecular sieve crystals having a plate-like morphology.

[0046] The synthetic mixture comprises at least one source of an oxide of a tetravalent element Y selected from the group consisting of Si, Ti, Zr, Sn, Ge, and mixtures thereof, preferably Y being Si and / or Ge, e.g., Si, and more preferably Y being Si and / or Ge, e.g., Si. The suitable source of the tetravalent element Y that can be used to make the synthetic mixture depends on the selected element Y. In embodiments where Y is silicon, suitable Si sources (e.g., silicon oxide sources) for use in this method include silicates, such as tetraalkyl orthosesilicates like tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS); fumed silica such as Aerosil® (commercially available from Evonik), Cabosperse® (commercially available from Cabot), and Cabosil® (commercially available from DMS); precipitated silica such as Ultrasil® and Sipernat® 340 (commercially available from Evonik); alkali metal silicates such as potassium silicate and sodium silicate; and aqueous colloidal suspensions of silica, such as those commercially available from Grace under the trade name Ludox® or from Evonik under the trade name Aerodisp®; preferably silicates, fumed silica, precipitated silica, faujasite zeolite, alkali metal silicates, and colloidal silica. In embodiments where Y is germanium, a suitable Ge source is germanium oxide. In embodiments where Y is titanium, suitable Ti sources include titanium dioxide and titanium tetraalkoxides such as titanium(IV) tetraethoxide and titanium(IV) tetrachloride. In embodiments where Y is tin, suitable tin sources include tin chloride, tin alkoxides such as tin ethoxide and tin isopropoxide. In embodiments where Y is zirconium, suitable Zr sources include zirconium chloride and zirconium alkoxides such as zirconium ethoxide and zirconium isopropoxide.

[0047] The synthetic mixture comprises at least one source of an oxide of a trivalent element X, which may be selected from the group consisting of Al, B, Fe, Ga, and mixtures thereof, preferably X is Al and / or B, e.g., Al, and more preferably X is Al and / or B, e.g., Al. The preferred source of the trivalent element X that can be used to make the synthetic mixture depends on the selected element X. In embodiments where X is aluminum, suitable aluminum sources for use in this method (e.g., aluminum oxide sources) include aluminum hydroxide, aluminum salts, especially water-soluble salts, e.g., alkali metal aluminates such as aluminum sulfate, aluminum nitrate, sodium aluminate, and aluminum alkoxides such as aluminum isopropoxide, as well as hydrated aluminum oxides such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other aluminum sources include, but are not limited to, other water-soluble aluminum salts, aluminum alkoxides such as sodium aluminate and aluminum isopropoxide, or aluminum metals such as chipped aluminum. Particularly suitable alumina sources are aluminum hydroxide; water-soluble salts such as aluminum sulfate and aluminum nitrate; and alkali metal aluminates such as sodium aluminate and potassium aluminate. In embodiments where X is boron, suitable boron sources include boric acid; borates such as sodium tetraborate or borax and potassium tetraborate. Boron sources tend to be more soluble than aluminum sources in hydroxide-mediated synthesis systems. In embodiments where X is gallium, suitable gallium sources include sodium gallate, potassium gallate, and gallium salts such as gallium chloride, gallium sulfate, and gallium nitrate. In embodiments where X is iron, suitable Fe sources include iron chloride, iron nitrate, and iron oxide.

[0048] In lieu of or in addition to the aforementioned sources of Y and X, a source containing both elements Y and X, such as a source of Si and Al, may be used. Examples of suitable sources containing both elements Si and Al include amorphous silica-alumina gel or dry silica-alumina powder, silica-alumina; clays such as kaolin and metakaolin; and zeolites, particularly aluminosilicates such as synthetic faujasite and ultrastable faujasite, such as Y-type zeolites, Ultrastable Y (USY), beta, or other large-pore to medium-pore zeolites.

[0049] The synthetic mixture may have a Y / X molar ratio (corresponding to the silicate product) ranging from 5 to infinity, for example, at least 5, or at least 7, or at least 10, and less than or equal to infinity, or less than or equal to 300, or less than or equal to 100, or less than or equal to 75, or less than or equal to 50, for example, from 10, or 15, or 20, to less than or equal to infinity, or less than or equal to 300, or less than or equal to 100, or less than or equal to 50.

[0050] In a preferred embodiment, Y is Si, X is optionally Al and / or B, and the molecular sieve is silicate, aluminosilicate, borosilicate, or aluminoborosilicate. In a further preferred embodiment, Y is Si, X is Al and / or B, and the molecular sieve is aluminosilicate, borosilicate, or aluminoborosilicate.

[0051] Optionally, the synthetic mixture may contain at least one source of hydroxide ions (OH). For example, hydroxide ions may be present as counterions to the structural indicator (Q) or by the use of aluminum hydroxide or sodium aluminate as an Al source. Suitable sources of hydroxide ions may be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; for example, from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more frequently from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most frequently, selected from the group consisting of sodium hydroxide and / or potassium hydroxide. The synthetic mixture may contain hydroxide ion sources with an OH / Y molar ratio of 0 to 1.0, e.g., 0.05 to 0.8, or 0.1 to 0.7, or 0.15 to 0.6, e.g., 0.25 to 0.5. Alternatively, the synthetic mixture may not contain substantially any hydroxide source.

[0052] Optionally, the synthetic mixture may contain one or more sources of alkali or alkaline earth metal cations (M). If present, M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, calcium, magnesium, and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. The sodium source, if present, may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or sodium salts such as NaCl, NaBr, or sodium nitrate. The potassium source, if present, may be potassium hydroxide, potassium aluminate, potassium silicate, potassium salts such as KCl, KBr, or potassium nitrate. The lithium source, if present, may be lithium hydroxide, or lithium salts such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. The rubidium source, if present, may be rubidium hydroxide, or rubidium salts such as RbCl, RbBr, RbI, or rubidium nitrate. The calcium source, if present, may be, for example, calcium hydroxide. The magnesium source, if present, may be, for example, magnesium hydroxide. Alkali or alkaline earth metal cations M may also be present in one or more sources of trivalent elements X, such as sodium aluminate, sodium tetraborate, and potassium tetraborate, and / or one or more sources of tetravalent elements Y, such as potassium silicate and / or sodium silicate. The synthetic mixture may contain alkali or alkaline earth metal cation (M) sources with an M / Y molar ratio of 0 to 1.0, e.g., 0.05 to 0.5 or 0.05 to 0.2, e.g., 0.1 to 0.15. Alternatively, the synthetic mixture may be substantially free of alkali or alkaline earth metal cations (M).

[0053] The synthetic mixture may optionally contain at least one fluoride ion source (F). The fluoride ion source (F) may be any compound capable of releasing fluoride ions into the molecular sieve synthetic mixture. For example, the fluoride ion may be present as a counterion of the structural indicator (Q). Non-limiting examples of sources of fluoride ions (F) include hydrogen fluoride (HF); salts containing one or more fluoride ions, preferably metal fluorides, where the metal is an alkali metal or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium, or barium, or a metal such as aluminum (AlF3, Al2F6) or tin (SnF2); ammonium fluoride (NH4F); and ammonium difluoride (NH4HF2). Particularly convenient fluoride ion sources are HF, NH4F, and NH4HF2, with HF being particularly useful. Small amounts of fluoride ions (F) may be present as impurities in any source of alkali or alkaline earth metal cations (M), for example. Fluoride ions (F) may be present in F / Y molar ratios of 0 to 1.0, e.g., 0 or 0.1 to 0.8, e.g., 0.2 to 0.7 or 0.3 to 0.6, e.g., 0.4 or 0.5. Alternatively, the synthetic mixture may be substantially free of fluoride ions (F).

[0054] The synthetic mixture may optionally further include at least one halide ion source (W) different from the fluoride ions, which may be selected from the group consisting of chlorides, bromides, or iodides. The halide ion source (W) may be any compound capable of releasing halide ions in the molecular sieve synthetic mixture. For example, the halide ions may be present as counterions to the structural indicator (Q). Non-limiting examples of halide ion sources include hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI); ammonium halides (e.g., NH4Cl, NH4Br, NH4I); salts containing one or more halide ions such as metal halides (preferably the metal being sodium, potassium, calcium, magnesium, strontium, or barium); or tetraalkylammonium halides such as tetramethylammonium halide or tetraethylammonium halide. Small amounts of halide ions (W) may be present as impurities in any source of alkali or alkaline earth metal cations (M), for example. Halide ions (W) may be present in a W / Y molar ratio of 0 to 0.2, e.g., 0 to 0.1, e.g., less than 0.1, or even 0. In preferred embodiments, the synthetic mixture may be substantially free of halide ions (W).

[0055] The synthesis may be carried out with or without the addition of nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds may have the same or different structure as the molecular sieves of this disclosure, for example, the EMM-74 material obtained from a previous synthesis, and may preferably be present in an amount of about 0.01 ppm by weight to about 10,000 ppm by weight relative to the synthesis mixture, for example, in an amount of about 100 ppm by weight to about 5,000 ppm by weight of the synthesis mixture.

[0056] The synthetic mixture typically contains water with an H2O / Y molar ratio of 1–100, e.g., 5–80 or 7.5–50, e.g., 7.5 or 10–40 or 35. Depending on the properties of the components in the base mixture, the amount of solvent in the base mixture (e.g., water from hydroxide solutions, optionally methanol and ethanol from hydrolysis of a silica source) may be removed to achieve the desired solvent / Y molar ratio for the synthetic mixture. Preferred methods for reducing the solvent content include evaporation under a static or fluid atmosphere such as ambient air, dry nitrogen, or dry air, or spray drying or freeze-drying. If too much water is removed during the solvent removal method, water may be added to the resulting mixture to achieve the desired H2O / Y molar ratio. In some examples, if the product has a sufficient H2O / Y molar ratio, water removal is not necessary.

[0057] Carbon in the form of CH2 may be present in various sources of components used to prepare the molecular sieves of this disclosure, for example, a tetravalent element source (silica source) or a trivalent element source (alumina source), and may be incorporated into the molecular sieve framework as a bridging atom. Nitrogen atoms may be incorporated into the molecular sieve framework as bridging atoms after the SDA has been removed.

[0058] In one or more embodiments, the solvent-prepared synthetic mixture (e.g., having achieved a desired water / silica ratio) may be mixed by mechanical means such as stirring or high-shear mixing to ensure suitable homogenization of the base mixture, for example, using a double asymmetric centrifugal mixer (e.g., a FlackTek speedmixer) with a mixing speed of 1000 rpm to 3000 rpm (e.g., 2000 rpm).

[0059] Next, the synthetic mixture is subjected to crystallization conditions suitable for molecular sieve formation. Crystallization of the molecular sieve may be carried out under static or agitated conditions in a suitable reaction vessel, such as a Teflon®-lined or stainless steel autoclave placed in a convection oven maintained at a suitable temperature.

[0060] Crystallization in step (b) of this method is typically carried out at a temperature of 100°C to 200°C, for example 120°C to 180°C, preferably 150°C to 170°C, for a sufficient time for crystallization to occur at the temperature used. For example, the crystallization time may be shortened at a higher temperature. For example, the crystallization conditions in step (b) of this method may include heating for a period of 1 to 100 days, for example 1 to 50 days, for example 1 to 30 days, for example at least 1 day or at least 4 days or at least 10 days, up to 40 days or up to 30 days or up to 21 days. The crystallization time may be determined by methods known in the art, for example, by sampling the synthetic mixture at various times, determining the yield and X-ray crystallinity of the precipitated solid. Unless otherwise indicated herein, the temperature measured is the temperature of the ambient environment surrounding the material being heated, for example, the temperature of the atmosphere in which the material is heated.

[0061] Typically, molecular sieves are formed in solution and may be recovered by standard means, such as centrifugation or filtration. The separated molecular sieves may be washed, recovered by centrifugation or filtration, and dried.

[0062] When the molecular sieves of this disclosure are used as adsorbents or catalysts in organic compound conversion methods, they may be at least partially dehydrated (e.g., dried). This may be done by heating them in an atmosphere such as air or nitrogen, at atmospheric pressure, sub-atmospheric pressure, or ultra-atmospheric pressure, at a temperature in the range of 80°C to 500°C, for example, in the range of 90°C to 370°C, for 30 minutes to 48 hours. Dehydration may also be done at room temperature by simply placing the molecular sieves in a vacuum, although a longer time is required to obtain a sufficient amount of dehydration.

[0063] The crystallization method ensures that the recovered product contains at least some of the structural indicator used in the synthesis within its pores. Therefore, the as-synthesized molecular sieves recovered from step (c) may be subjected to heat treatment or other treatments to remove some or all of the SDA incorporated into their pores during synthesis. Heat treatment (e.g., calcination) of the as-synthesized molecular sieves typically involves exposing the material to a temperature high enough to remove some or all of the SDA in a furnace in an atmosphere selected from air, nitrogen, ozone, or a mixture thereof. While subatmospheric pressure may be used for the heat treatment, atmospheric pressure is preferred for convenience. The heat treatment may be carried out at temperatures below 925°C, e.g., 300°C–700°C or 400°C–600°C. The temperature measured is the ambient temperature of the sample. The heat treatment (e.g., calcination) may be carried out in a box furnace in dry air exposed to a drying tube containing a desiccant to remove moisture from the air. Heating typically lasts for at least one minute, and generally for no more than one day, or at most several days. Heating may initially be carried out under a nitrogen atmosphere, after which the atmosphere may be switched to air and / or ozone.

[0064] Molecular sieves may also be subjected to ion exchange treatment with aqueous ammonium salts, such as ammonium nitrate, ammonium chloride, or ammonium acetate, to remove any remaining alkali metal cations and / or alkaline earth metal cations present in the synthetic mixture, and to replace them with protons, thereby producing an acidic form of the molecular sieve. To a desired extent, the original cations of the as-synthesized material, such as alkali metal cations, may be replaced by ion exchange with other cations. Preferred substituted cations include hydrogen ions, hydrogen precursors, such as ammonium ions, and mixtures thereof. The ion exchange step may be performed after the as-produced molecular sieve has been dried. The ion exchange step may be performed either before or after the calcination step.

[0065] Optionally, aluminum atoms may be introduced into the molecular sieve framework (with some or all of the SDA removed) during an exchange step following the hydrothermal synthesis reaction. Framework silicates containing boron atoms (e.g., borosilicate) may be particularly effective for exchange with aluminum atoms. Such an exchange step may involve exposing the molecular sieve to an aluminum source, such as an aqueous solution containing an aluminum salt, under conditions sufficient to exchange at least some and substantially all of the boron atoms in the framework silicate with aluminum atoms. For example, calcined molecular sieves containing boron may be converted to aluminosilicate molecular sieves by heating them with a solution of aluminum sulfate, aluminum nitrate, aluminum chloride and / or aluminum acetate (e.g., in a sealed autoclave in a convention oven at 100°C or at the boiling point in an open system). The aluminum-treated molecular sieves may then be recovered by filtration and washed with deionized water.

[0066] Molecular sieves can also be subjected to other treatments such as steam treatment and / or solvent washing. Such treatments are well known to those skilled in the art and are performed to modify the properties of the molecular sieves to a desired extent.

[0067] Molecular sieves of the present disclosure, from which some or all of the SDA has been removed, may be used as adsorbents or as catalysts or catalytic carriers in a wide variety of hydrocarbon conversions, such as the conversion of organic compounds into conversion products. In a fourth aspect, the present disclosure thus relates to a method for converting organic compounds into conversion products, the method comprising contacting the organic compound with a molecular sieve according to the first or second aspect of the present disclosure, or preparing it according to the method of the third aspect of the present disclosure.

[0068] The molecular sieve of this disclosure (with some or all of the SDA removed) may be used as an adsorbent, for example, to separate at least one component from a mixture of gaseous or liquid-phase components having differential sorption properties with respect to a material. Thus, by contacting the molecular sieve with the mixture to selectively adsorb one component, it is possible to partially or substantially completely separate at least one component from a mixture of components having differential sorption properties with respect to the molecular sieve. For example, in a method for selectively separating one or more desired components of a feedstock from the remaining components of the feedstock, the feedstock may be contacted with an sorbent comprising the molecular sieve of this disclosure under effective sorption conditions, thereby forming sorption products and efflux products. One or more desired components are recovered from either the sorption products or the efflux products.

[0069] The molecular sieves of this disclosure (with some or all of the SDA removed) may also be used as catalysts for catalyzing a wide variety of organic compound transformation methods. Examples of chemical transformation methods that can be effectively catalyzed by the molecular sieves described herein, either alone or in combination with one or more other catalytically active substances, including other crystalline catalysts, include those requiring an acid-active catalyst. Examples of organic transformation methods that may be catalyzed by the molecular sieves described herein include decomposition, hydrocracking, isomerization, polymerization, modification, hydrogenation, dehydrogenation, dewaxing, hydrodeswaxing, adsorption, alkylation, transalkylation, dealkylation, hydrodesilylation, disproportionation, oligomerization, dehydrogenation, cyclization, methanol to olefin conversion, denitrification, and combinations thereof. The transformation of hydrocarbon feedstocks may be carried out in any convenient form, such as a fluidized bed, moving bed, or fixed-bed reactor, depending on the type of method desired.

[0070] The molecular sieves of this disclosure may be incorporated into product compositions in combination with other materials, such as binders and / or matrix materials, to provide additional hardness to the final product. These other materials may be inert or catalytic materials.

[0071] For example, it may be desirable to combine the molecular sieves of this disclosure with other materials that are resistant to the temperatures and other conditions employed during use. Such materials include synthetic or naturally occurring zeolites, as well as inorganic materials such as clay, silica and / or alumina and mixtures thereof, and metal oxides. Metal oxides may be naturally occurring or may be in the form of gel-like precipitates or gels containing mixtures of silica and metal oxides. When resistant materials are used in combination with the molecular sieves of this disclosure, i.e., in combination with or present in the synthesis of as-produced molecular sieves in which the crystals are active, the conversion and / or selectivity of the catalyst in a particular organic conversion method tends to change. Inert resistant materials are suitably used as diluents for controlling the amount of conversion in a given method, so that the product can be obtained in an economical and orderly manner without employing other means to control the reaction rate. These materials may be incorporated into naturally occurring clays, such as bentonite and kaolin, to improve the fracturing strength of the product under commercial operating conditions. The inert resistant materials, i.e., clay, oxides, etc., function as a binder for the catalyst. In commercial use, it is desirable to prevent the catalyst from decomposing into a powdery substance, so a catalyst with good grinding strength may be beneficial.

[0072] Naturally occurring clays that may be used include montmorillonite and kaolin family, and these families include sub-bentonite, and kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others whose main mineral component is halloysite, kaolinite, dickite, nacrite, or anaxite. Such clays can be used as mined in the raw state or after being calcined, acid-treated, or chemically modified. Useful binders for complexing with the molecular sieves of the present disclosure also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallium oxide, zinc oxide, and mixtures thereof.

[0073] In addition to the foregoing materials, the molecular sieves of the present disclosure may be complexed with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

[0074] These binder materials are resistant to the temperatures and other conditions, such as mechanical wear, that occur in various hydrocarbon separation processes. Thus, the molecular sieves of the present disclosure may be used in the form of an extrudate having a binder. These are typically bound by forming tablets, spheres, or extrudates. Extrudates are usually formed by extruding the molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudate. If necessary, treatments such as steam treatment, ion exchange, etc. may be carried out. The molecular sieve may optionally have a surface area of at least 100 m 2 / g, for example at least 200 m 2 / g, optionally at least 300 m 2 / g and be combined with a binder.

[0075] The relative ratio of molecular sieves to inorganic oxide matrix can vary widely, with molecular sieve content ranging from approximately 1% to approximately 100% by weight, and more commonly, particularly when the composite is manufactured in the form of an extruded product, from approximately 2% to approximately 95% by weight, and optionally from approximately 20% to approximately 90% by weight of the composite.

[0076] The molecular sieves of this disclosure may also be used in close combination with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as platinum or palladium, when hydrogenation-dehydrogenation functions are performed. Such hydrogenation components can be incorporated into the composition by one or more steps of cocrystallization; replacement in the composition to the extent that a group IIIA element, such as aluminum, is present in the structure; or close physical miscion with it. Such components can also be impregnated into or onto the molecular sieves, for example, by treating the molecular sieves with metal hydride-containing ions. For example, in the case of platinum, suitable platinum compounds for this purpose include a variety of compounds including chloroplatinic acid, chlorplatinic acid, and platinumamine complexes. Combinations of metals and methods for introducing them can also be used.

[0077] Those skilled in the art will understand that the molecular sieves of this disclosure may contain impurities such as amorphous materials, unit cells having different topologies (e.g., quartz or different framework-type molecular sieves that may or may not affect the performance of the resulting catalyst), and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). Typical examples of different framework-type molecular sieves coexisting with the molecular sieves of this disclosure are, for example, ferrielite or FER framework-type molecular sieves such as ZSM-35. The molecular sieves of this disclosure are preferably substantially free of impurities. As used herein, the term “substantially free of impurities” (or alternatively “substantially pure”) means that molecular sieves are present in small proportions (less than 50 wt%), preferably less than 20 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%, and most preferably less than 1 wt% (e.g., the weight percentage (wt%) of impurities (e.g., “non-EMM-74 material”) is based on the total weight of impurities and pure molecular sieves. The amount of impurities can be appropriately determined by powder XRD, rotational electron diffraction, and / or SEM / TEM (e.g., different crystalline forms).

[0078] The molecular sieves described herein are substantially crystalline. As used herein, the term “crystalline” refers to a crystalline solid form of a material, including, but not limited to, single-component or multi-component crystalline forms, such as solvates, hydrates, and cocrystals. Crystallinity can mean having a regular repeating and / or regular arrangement of molecules and having a recognizable crystalline lattice. For example, molecular sieves may have different water or solvent content. Different crystalline lattices can be identified by solid-state characterization methods such as XRD (e.g., powder XRD). Other characterization methods known to the ordinary art in the relevant field may be helpful not only in determining stability and solvent / water content but also in identifying crystalline forms. As used herein, the term “substantially crystalline” means that the majority (more than 50% by weight) of a sample of the material described is crystalline, and the remainder of the sample is in an amorphous form. In one or more embodiments, a substantially crystalline sample has a crystallinity of at least 95% (e.g., 5% in amorphous form), at least 96% (e.g., 4% in amorphous form), at least 97% (e.g., 3% in amorphous form), at least 98% (e.g., about 2% in amorphous form), at least 99% (e.g., 1% in amorphous form), and 100% (e.g., 0% in amorphous form).

[0079] The aspects of this disclosure will be described in more detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit this disclosure in any way. Those skilled in the art will readily recognize that various parameters can be changed or modified to obtain essentially the same results. [Examples]

[0080] The present invention will be further described below without limiting its scope.

[0081] In these examples, X-ray diffraction (XRD) patterns of the as-synthesized and fired materials were recorded in continuous mode over a 2θ range of 2–50° using Cu(Kα) radiation and Bragg-Bentano geometry, with a Vantec 500 detector on an X-ray powder diffractometer (Bruker DaVInci D8 Discovery instrument). Interplane spacing and d-spacing were calculated in angstroms, and the relative line intensity, I / Io, is the ratio of the peak intensity to the intensity of the strongest line above the background. Intensities are not corrected for Lorentz effects or polarization effects. The position of the diffraction peak at 2θ and the relative peak area intensity I / I(o) (where Io is the intensity of the line stronger than the background) were determined using the MDI Jade peak detection algorithm. It should be understood that diffraction data described as a single line may consist of multiple overlapping lines that appear as resolved or partially resolved lines under certain conditions, such as differences in crystallographic changes. Typically, crystallographic changes include minor changes in unit cell parameters and / or changes in crystal symmetry, while the connectivity of the framework remains unchanged. These minor effects, including changes in relative intensity, may also result from differences in cation content, framework composition, pore filling properties and degree, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0082] Scanning electron microscope (SEM) images of the as-synthesized material were obtained using a Hitachi 4800 scanning electron microscope. The SEM images were used to assess the purity of the product. The presence of distinctly different crystalline morphologies in the SEM images may indicate the presence of impurities in the form of other crystalline substances. Such approximate analysis is particularly useful in identifying the presence of relatively small amounts of crystalline impurities that may not be discernible in the XRD pattern of the product.

[0083] The overall BET surface area of ​​the material (S BETThe external surface area (S) of the material is described in S. Brunauer, et al. (1938) "Adsorption of Gases in Multimolecular Layers," J. Am. Chem. Soc., v.60(2), pp. 309-319, which is incorporated herein by reference. ext ) is obtained from the t-plot method, and the micropore surface area (S) of the material is obtained from the t-plot method. micro ) is the total BET surface area (S BET ) from the external surface area (S ext It was calculated by subtracting ).

[0084] Material's micropore volume (V micro ) and total pore volume (V tot ) can be determined using methods known in the relevant technical field. For example, the micropore volume and total pore volume of a material can be measured by nitrogen physicoadsorption, and the data can be analyzed by the t-plot method described in BC et al. (1965) "Studies on Pore System in Catalysts: V. The t Method", J. Catal., v.4(3), pp. 319-323.

[0085] The molar ratios and conditions used in the synthesis of Examples 2 to 14, as well as the resulting products, are described in detail below and summarized in Table 3.

[0086] (Example 1a): Synthesis of 1-methylimidazo[1,2-a]pyridine-1-ium cation (SDA-1) A mixture of 1-methylimidazo[1,2-a]pyridine-1-ium iodide (25 g, 211.61 mmol) and methyl iodide (69.08 g, 486.71 mmol) in 265 mL of acetonitrile was heated at 80°C for 10 hours. Thin-layer chromatography showed the remaining starting material after 10 hours. The reaction mixture was cooled to room temperature, and the acetonitrile was removed using a rotary evaporator (rotovap). The resulting yellow oil was triturated with 200 mL of ethyl acetate, and the yellow solid was recovered. 1 1H-NMR showed the presence of the desired product and impurities. The impurities were removed by heating the yellow solid in 200 mL of acetone to 50°C and filtering the remaining solid. 1 1H-NMR confirmed that a clean, desired product was obtained.

[0087] The 1-methylimidazo[1,2-a]pyridine-1-ium hydroxide:iodide salt was ion-exchanged to its hydroxide form using the ion-exchange resin Amberlite® IRN78 OH (iodide:resin:water ratio 1:3.5:5). The exchange was carried out overnight at room temperature.

[0088] (Example 1b): Synthesis of 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation (SDA-2) 1,2-dimethylimidazo[1,2-a]pyridine-1-ium iodide: A mixture of 26.52 g (200.65 mmol) of 2-methylimidazo[1,2-a]pyridine and 29.90 g (210.68 mmol) of methyl iodide in 250 mL of acetonitrile was stirred at room temperature for 16 hours. The solid was filtered and washed with 200 mL of ethyl acetate. 1 The sample was air-dried for 30 minutes before taking the 1H-NMR spectrum. 1 1H-NMR confirmed that a clean, desired product was obtained.

[0089] The 1,2-dimethylimidazo[1,2-a]pyridine-1-ium hydroxide:iodide salt was ion-exchanged to its hydroxide form using the ion-exchange resin Amberlite® IRN78 OH (iodide:resin:water ratio 1:3.5:5). The exchange was carried out overnight at room temperature.

[0090] (Example 1c): Synthesis of 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation (SDA-3) 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium iodide: 25.0 g (221.6 mmol) of 1H-pyrrolo[3,2-c]pyridine, 69.1 g (486.7 mmol) of methyl iodide, and 13.1 g (232.8 mmol) of potassium hydroxide were heated in 400 mL of acetonitrile at 80°C for 6 hours. The acetonitrile was removed using a rotary evaporator (rotavap), and the residue was dissolved in 250 mL of chloroform. The potassium salt was removed by filtration, and then the chloroform was removed using a rotary evaporator. The residue was triturated with 350 mL of ethyl acetate, and the product precipitated as a mustard-colored solid. The solid was collected and air-dried for 30 minutes. 1 As confirmed by 1H-NMR, 55.5 g (96%) of 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-iodine iodide was obtained.

[0091] The 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium hydroxide:iodide salt was ion-exchanged to its hydroxide form using the ion-exchange resin Amberlite® IRN78 OH (iodide:resin:water ratio 1:3.5:5). The exchange was carried out overnight at room temperature.

[0092] (Example 1d): Synthesis of 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation (SDA-4) 1,6-dimethylimidazo[1,2-a]pyridine-1-ium iodide: 25 g (189.15 mmol) of 6-methylimidazo[1,2-a]pyridine was stirred in 236 mL of acetonitrile, to which 53.7 g (378.3 mmol) of methyl iodide was added dropwise at room temperature. The reaction was monitored by thin-layer chromatography (TLC). After the 6-methylimidazo[1,2-a]pyridine disappeared, ether was added and a solid was formed. The solid was recovered by filtration, washed with 300 mL of ether, and air-dried. This reaction yielded, 1 As confirmed by 1H-NMR, 439 g of the desired product was obtained.

[0093] The 1,6-dimethylimidazo[1,2-a]pyridine-1-ium hydroxide:iodide salt was ion-exchanged to its hydroxide form using the ion-exchange resin Amberlite® IRN78 OH (iodide:resin:water ratio 1:3.5:5). The exchange was carried out overnight at room temperature.

[0094] (Example 1e): Synthesis of 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium cation (SDA-5) 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium iodide: 18.7 g of 4-azaindole, 52 g of methyl iodide, and 10.0 g of potassium hydroxide were heated overnight at 70°C in 200 mL of acetonitrile. The acetonitrile was removed using a rotary evaporator, and the residue was dissolved in chloroform. 1 ¹H-NMR revealed a brown solid 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium iodide (or 1,4-dimethyl-4-azaindrium iodide).

[0095] The 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium hydroxide:iodide salt was ion-exchanged to its hydroxide form using the ion-exchange resin Amberlite® IRN78 OH (iodide:resin:water ratio of 1:3.5:5). The exchange was carried out overnight at room temperature.

[0096] (Example 2): SDA-2, USY zeolite, NaOH, Si / Al=15 In a PTFE liner for a 10 mL Steel Parr autoclave, the following was mixed: 2.7 g of 1,2-dimethylimidazo[1,2-a]pyridine-1-ium(SDA-2) hydroxide solution (5.9 wt%), 0.96 g of NaOH aqueous solution (4 wt%), and 0.46 g of Ultrastable Y(USY) zeolite with a Si / Al molar ratio of 15 (commercially available from Zeolyst as CBV720) to prepare a synthetic mixture with the following molar composition: 30 H2O:1 SiO2:0.033 Al2O3:0.15 QOH:0.15 NaOH.

[0097] Next, the liner was capped and sealed inside a 10 mL Parr autoclave, which was then placed in a pit in a convection oven. The reactor was heated at 160°C for one week under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, washed with deionized water, and dried at 90°C in an air-drying oven. The as-synthesized material was then calcined in a box furnace in air at a heating rate of 3°C / min to 580°C. The temperature was maintained at 580°C for 8 hours, after which the box furnace was cooled.

[0098] XRD analysis of the as-synthesized and calcined products revealed that this material was similar to the powder XRD patterns of the as-synthesized and calcined SSZ-48 molecular sieves in terms of 2θ angles and d-spacing, but differed in relative intensity (for example, as shown in Tables I and II of U.S. Patent No. 6,080,382, which is incorporated herein by reference in its entirety). This new product was identified as EMM-74. Figures 1 and 2 show the powder XRD patterns of the as-synthesized and calcined EMM-74 materials of Example 2. Tables 4 and 5 below list the peaks and intensities of the as-synthesized and calcined EMM-74 materials or Example 2.

[0099] The EMM-74 material was shown to have an SFE framework type with a 12-membered ring pore channel (12MR) having dimensions of 5.4 Å × 7.6 Å.

[0100] The EMM-74 material had a uniform rod-like morphology with a particle diffusion length of approximately 300 nm, a diameter (or width or thickness) of approximately 50 nm, and an aspect ratio (l / d) of approximately 6, as shown in Figure 3, which shows an SEM image of the as-synthesized product of Example 2.

[0101] The fired EMM-74 material is 302m 2 Micropore surface area (S) / g micro ), 53m 2 External surface area (S) ext ), 0.31cm 3 Total pore volume (V) / g tot ), and 0.12cm 3 Micropore volume (V) / g micro It possessed the following adsorption amounts: n-hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and mesitylene were 73 mg / g, 67 mg / g, 57 mg / g, and 59 mg / g, respectively. These data indicate that much of the micropore volume of EMM-74 is available for these adsorbed molecules. The pore channels of 12MR are clearly large enough to accommodate 1,3,5-trimethylbenzene (mesitylene), and similarly, the capacity for smaller adsorbents.

[0102] (Example 3): SDA-2, USY zeolite, sodium aluminate, NaOH, Si / Al = 16.5 In this example, an Ultrastable Y(USY) zeolite with a Si / Al molar ratio of 30 (commercially available from Zeolyst as CBV760) and sodium aluminate (NaAlO2, 25 wt% Al2O3, 19.3 wt% Na2O) were used as Si and Al sources, resulting in the following molar composition: 30H2O:1SiO2:0.03Al2O3:0.15QOH:0.15NaOH.

[0103] After heating at 160°C for 10 days, a pure EMM-74 product was obtained, as identified by XRD pattern analysis. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0104] (Example 4): SDA-2, USY zeolite, sodium aluminate, NaOH, Si / Al=25 This example was carried out under the same conditions as Example 3, except that the synthesis mixture contained less Al and less NaOH, resulting in the following molar ratio composition: 30H2O:1SiO2:0.02Al2O3:0.15QOH:0.1NaOH.

[0105] After heating at 160°C for 10 days, a pure EMM-74 product was obtained, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0106] (Example 5): SDA-2, colloidal silica, sodium aluminate, NaOH, Si / Al=15 This example was carried out under the same conditions as in Example 3, except that Ludox HS40 (40 wt% colloidal silica suspension) was used as the Si source and sodium aluminate (NaAlO2, 25 wt% Al2O3, 19.3 wt% Na2O) was used as the Al source, and a synthetic mixture having the following molar composition was obtained: 33H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0107] After heating at 160°C for three weeks, an EMM-74 product containing a small amount of FER material was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0108] (Example 6): SDA-2, colloidal silica, sodium aluminate, NaOH, Si / Al = 22.5 This example was carried out under the same conditions as in Example 5, except that the synthetic mixture contained smaller amounts of Al and NaOH, and as a result, a synthetic mixture having the following molar composition was obtained: 33H2O:1SiO2:0.022Al2O3:0.15QOH:0.10NaOH.

[0109] After heating at 160°C for 3 weeks, an EMM-74 product was obtained that contained a small amount of amorphous phase material, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0110] (Example 7): SDA-2, USY zeolite, KOH, Si / Al=15 This example was carried out under the same conditions as Example 2, except that NaOH was replaced with KOH (20%), and the synthetic mixture also contained a smaller amount of water, resulting in a synthetic mixture having the following composition in terms of molar ratio: 22 H2O:1 SiO2:0.033 Al2O3:0.15 QOH:0.15 KOH.

[0111] After heating at 160°C for one week, a pure EMM-74 product was obtained, as identified by XRD pattern analysis.

[0112] The EMM-74 material of Example 7 had a uniform rod-like morphology with a particle diffusion length of approximately 50–200 nm, a diameter (or width or thickness) of approximately 20–50 nm, and an aspect ratio (l / d) of approximately 2–8, as shown in Figure 4, which shows an SEM image of the as-synthesized product of Example 7.

[0113] (Example 8): SDA-2, USY zeolite, KOH, Si / Al=30 This example was carried out under the same conditions as in Example 7, except that it used Ultrastable Y(USY) zeolite (commercially available from Zeolyst as CBV760) with a Si / Al molar ratio of 30 as the Si and Al source, and the synthesized mixture also contained a larger amount of water and a smaller amount of KOH, resulting in the following composition in terms of molar ratio: 30H2O:1SiO2:0.017Al2O3:0.15QOH:0.1KOH.

[0114] After heating at 160°C for two weeks, a pure EMM-74 product was obtained, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0115] (Example 9): SDA-2, USY zeolite, KOH, Si / Al=40 This example was carried out under the same conditions as Example 8, except that the synthesis mixture contained a smaller amount of Al. Ultrastable Y(USY) zeolite (commercially available from Zeolyst as CBV780) with a Si / Al molar ratio of 40 was used as the Si and Al source, resulting in the following composition in terms of molar ratio: 30H2O:1SiO2:0.0125Al2O3:0.15QOH:0.1KOH.

[0116] After heating at 160°C for two weeks, an EMM-74 product containing a small amount of quartz was obtained, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0117] (Example 10): SDA-2, TEOS, aluminum hydroxide, HF, Si / Al=25 1.43 g of tetraethyl orthosilicate (TEOS, >99 wt%) and 0.026 g of aluminum hydroxide (Sigma, 54 wt% Al2O3) were hydrolyzed in 9.6 g of 1,2-dimethylimidazo[1,2-a]pyridine-1-ium (SDA-2) hydroxide solution (5.9 wt%) at room temperature for approximately 2-3 hours. The mixture was then heated to approximately 50°C to remove ethanol and water. Subsequently, 0.14 HF (48 wt% solution) was added to the mixture to prepare a synthetic mixture having the following molar composition: 7.5H2O:1SiO2:0.02Al2O3:0.5QOH:0.5HF.

[0118] The resulting concentrated paste was homogenized by hand and transferred to a PTFE liner for a 10 mL Steel Parr autoclave. The reactor was heated at 160°C for 3 weeks under tumbling conditions (approximately 40 rpm). The product was isolated by centrifugation, washed three times with distilled water (100 mL), and dried at 90°C in a vented drying oven. The as-synthesized material was then calcined in a box furnace in air at a heating rate of 3°C / min to 580°C. The temperature was maintained at 580°C for 8 hours, after which the box furnace was cooled.

[0119] XRD analysis of the as-synthesized product indicated that the material was a pure EMM-74 product. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0120] (Example 11): SDA-2, TEOS, aluminum hydroxide, HF, Si / Al=50 This example was carried out under the same conditions as Example 10, except that the synthetic mixture contained less Al and more water, resulting in the following molar ratio composition: 15H2O:1SiO2:0.01Al2O3:0.5QOH:0.5HF.

[0121] After heating at 160°C for three weeks, an EMM-74 product was obtained containing small amounts of unidentified impurities, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0122] (Example 12): SDA-1, TEOS, aluminum hydroxide, HF, Si / Al=50 This example uses SDA-2 hydroxide instead of The procedure was carried out under the same conditions as in Example 11, except that 1-methylimidazo[1,2-a]pyridine-1-ium(SDA-1) hydroxide was used. The synthesized mixture had the following molar composition: 15H2O:1SiO2:0.01Al2O3:0.5QOH:0.5HF.

[0123] After heating at 160°C for 10 days, a pure EMM-74 product was obtained, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0124] (Example 13): SDA-4, USY zeolite, NaOH, Si / Al=15 Following the same procedure as in Example 2, the following was mixed in a PTFE liner for a 10 mL Steel Parr autoclave: 1.41 g of 1,6-dimethylimidazo[1,2-a]pyridine-1-ium(SDA-4) hydroxide solution (15 wt%), 0.51 g of NaOH solution (10 wt%), 2.9 g of deionized water, and 0.61 g of Ultrastable Y(USY) zeolite with a Si / Al molar ratio of 15 (commercially available from Zeolyst as CBV720) to produce a synthetic mixture having the following molar composition: 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0125] Next, the liner was capped and sealed in a 10 mL Parr autoclave, which was then placed in a pit in a convection oven under tumbling conditions (approximately 30 rpm). After heating at 160°C for 20 days, a pure EMM-74 product was obtained, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0126] (Example 14): SDA-3, USY zeolite, NaOH, Si / Al=15 Similar to the procedure in Example 2, the following were mixed together in a PTFE liner for a 10 mL Steel Parr autoclave: 3.8 g of 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium (SDA-3) hydroxide solution (5.5 wt%), 0.51 g of NaOH solution (10 wt%), and 0.61 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (commercially available from Zeolyst as CBV720) to produce a synthetic mixture having the following molar composition: 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0127] Next, the liner was capped and sealed inside a 10 mL Parr autoclave, which was then placed in a pit in a convection oven. The reactor was heated at 160°C for 10 days under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, washed with deionized water, and dried at 90°C in an air-drying oven. The as-synthesized material was then calcined in a box furnace in air at a heating rate of 3°C / min to 580°C. The temperature was maintained at 580°C for 8 hours, after which the box furnace was cooled.

[0128] XRD analysis of the as-synthesized product indicated that the material was a pure EMM-74 product. As shown in Figure 5, which shows an SEM image of the as-synthesized product of Example 14, the EMM-74 aluminosilicate of Example 14, prepared using SDA-3, has a uniform plate-like morphology with a length of approximately 100–150 nm, a width of 50–100 nm, and a thickness of approximately 20–30 nm.

[0129] (Example 15): SDA-3, USY zeolite, NaOH, Si / Al=15 Example 14 was reproduced with a slightly reduced amount of water, resulting in a synthetic mixture having the following molar ratio: 27H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0130] After heating at 170°C for 10 days, a pure EMM-74 product was obtained, as identified by XRD patterning. The EMM-74 product had a plate-like morphology similar to that of the product in Example 14, as determined by SEM.

[0131] (Example 16): SDA-3, colloidal silica, aluminum hydroxide, NaOH, Si / Al=20 This example was carried out under the same conditions as in Example 14, except that Ludox AS40 (40 wt% colloidal silica suspension) was used as the Si source and aluminum hydroxide (Sigma, 54 wt% Al2O3) was used as the Al source, and a synthetic mixture having the following molar composition was obtained: 30H2O:1SiO2:0.025Al2O3:0.15QOH:0.15NaOH.

[0132] After heating at 160°C for 10 days, an EMM-74 product containing a small amount of FER material was obtained, as identified by its XRD pattern. The EMM-74 product had a plate-like morphology similar to that of the product in Example 14, as determined by SEM.

[0133] (Example 17): SDA-2, colloidal silica, boric acid, Si / B=10 In a PTFE liner for a 10 mL Steel Parr autoclave, the following were mixed together: 8.6 g of 1,2-dimethylimidazo[1,2-a]pyridine-1-ium(SDA-2) hydroxide solution (5.9 wt%), 1.16 g of Ludox HS40 (40 wt% colloidal silica suspension), and 1.23 g of boric acid (3.87 wt% H3BO3 solution). The mixture was then vaporized to produce a synthetic mixture with the following molar ratio composition: 10H2O:1SiO2:0.05B2O3:0.4QOH.

[0134] Next, the liner was capped and sealed inside a 10 mL Parr autoclave, which was then placed in a pit in a convection oven. The reactor was heated at 160°C for 3 weeks under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, washed with deionized water, and dried at 90°C in an air-drying oven. The as-synthesized material was then calcined in a box furnace in air at a heating rate of 3°C / min to 580°C. The temperature was maintained at 580°C for 8 hours, after which the box furnace was cooled.

[0135] Figures 6 and 7 show the powder XRD patterns of the as-synthesized and calcined materials, corresponding to the pure EMM-74 product. Tables 6 and 7 below list the peaks and intensities of the as-synthesized and calcined EMM-74 materials for Example 17.

[0136] As shown in Figure 8, which displays an SEM image of the as-synthesized product of Example 17, the EMM-74 borosilicate of Example 17 had a uniform rod-like morphology similar to the product of Example 2, with a particle diffusion length of approximately 300 nm and a diameter (or width or thickness) of approximately 50 nm.

[0137] (Example 18): SDA-2, Y-type zeolite, boric acid, NaOH, Si / B=16.5, Si / Al=50 This example was carried out under the same conditions as in Example 3, except that a Y-type zeolite with a Si / Al molar ratio of 50 (commercially available from Tosoh as HSZ-385HUA) was used as the source of Si and Al, and boric acid was added as the source of B (3.87 wt% H3BO3 solution), resulting in the following molar composition: 30H2O:1SiO2:0.03B2O3:0.01Al2O3:0.15QOH:0.15NaOH.

[0138] After heating at 160°C for 10 days, a pure aluminoborosilicate EMM-74 product was obtained, as identified by XRD patterning. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0139] (Example 19): SDA-2, Y-type zeolite, boric acid, NaOH, Si / B=10, Si / Al=250 This example was carried out under the same conditions as Example 18, except that the synthesis mixture contained less water, more boron, and less aluminum, and a Y-type zeolite with a Si / Al molar ratio of 250 (commercially available from Tosoh as HSZ-390HUA) was used as the source of Si and Al, resulting in the following composition in terms of molar ratios: 25H2O:1SiO2:0.05B2O3:0.002Al2O3:0.15QOH:0.15NaOH.

[0140] After heating at 160°C for 6 days, a pure EMM-74 product was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product in Example 2, as determined by SEM.

[0141] (Example 20): SDA-5, USY zeolite, KOH, Si / Al=15 In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 3.1 g of 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium (SDA-5) hydroxide solution (9.4 wt%), 0.36 g of KOH solution (20 wt%), 2.25 g of deionized water, and 0.61 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (commercially available from Zeolyst as CBV720) to produce a synthetic mixture with the following molar composition: 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15KOH.

[0142] Next, the liner was capped and sealed inside a 23 mL Parr autoclave, which was then placed in a spit in a convection oven. The reactor was heated at 160°C for 8 days under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, washed with deionized water, and dried.

[0143] XRD analysis of the as-synthesized product indicated that the material was a pure EMM-74 product. JPEG2026509429000015.jpg105165 SDA-2=1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation SDA-3=1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation SDA-4=1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation SDA-5=1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium cation JPEG2026509429000016.jpg107105 JPEG2026509429000017.jpg120119 JPEG2026509429000018.jpg120115 JPEG2026509429000019.jpg113111

[0144] While the present invention has been described and explained with reference to specific embodiments, it will be understood by those skilled in the art that the invention is suitable for many different changes, modifications, and variations not specifically described herein. It will also be apparent to those skilled in the art that where numerical lower and upper limits are given herein, a range from any lower limit to any upper limit is intended. Furthermore, all numerical values ​​in the detailed descriptions herein have been modified by values ​​indicated as "approximately" to take into account the experimental errors and variations expected by those skilled in the art.

[0145] Where any integer or element having known, obvious, or foreseeable equivalents is mentioned in the foregoing description, such equivalents are incorporated herein as if they were individually described. The claims should be referred to in order to determine the true scope of the invention, but the claims should be interpreted to encompass such equivalents. It will also be understood by the reader that any integer or feature of the invention described as preferred, advantageous, convenient, etc., is optional and does not limit the scope of the independent claims. Furthermore, it will be understood that such any integer or feature may be beneficial in some embodiments of the invention, while being undesirable and therefore absent in other embodiments.

[0146] Furthermore, or alternatively, the present invention relates to the following: Embodiment 1: A molecular sieve having an X-ray diffraction pattern including the peaks shown in Table 1 in the firing configuration. Embodiment 2: Formula V: (m)X2O3:YO2 (Formula V) (In the formula, 0 ≤ m ≤ 0.1, X is a trivalent element, and Y is a tetravalent element.) Molecular sieve of Embodiment 1 having the molecular formula, Here, Embodiment 3: The molecular sieve according to Embodiment 2, wherein X comprises one or more of aluminum, boron, iron, and gallium, preferably X comprises aluminum and / or boron, or is aluminum and / or boron. Embodiment 4: The molecular sieve according to Embodiment 2 or 3, wherein Y comprises one or more of silicon, titanium, zirconium, tin, and germanium, preferably Y comprises silicon and / or germanium, or silicon and / or germanium, and more preferably silicon. Embodiment 5: A molecular sieve having an X-ray diffraction pattern in its as-synthesized form that includes the peaks shown in Table 2. Embodiment 6: Formula VI below: (q)Q:(m)X2O3:YO2(Formula VI) (In the formula, 0 <q≦0.7、0≦m≦0.1であり、xは3価の元素であり、yは4価の元素であり、qは、式iの1‐メチルイミダゾ[1,2‐a]ピリジン‐1‐イウムカチオン、式iiの1,2‐ジメチルイミダゾ[1,2‐a]ピリジン‐1‐イウムカチオン、式iiiの1,5‐ジメチル‐1h‐ピロロ[3,2‐c]ピリジン‐5‐イウムカチオン、式ivの1,6‐ジメチルイミダゾ[1,2‐a]ピリジン‐1‐イウムカチオン、および式vの1,4‐ジメチル‐1h‐ピロロ[3,2‐b]ピリジン‐4‐イウムから選択される少なくとも1つのカチオンを含む:JPEG2026509429000020.jpg135131 A molecular sieve according to Embodiment 5 having the molecular formula. Embodiment 7: The molecular sieve according to Embodiment 6, wherein X comprises one or more of aluminum, boron, iron, and gallium, preferably comprising aluminum and / or boron, or aluminum and / or boron. Embodiment 8: The molecular sieve according to Embodiment 6 or 7, wherein Y comprises one or more of silicon, titanium, zirconium, tin, and germanium, preferably Y comprises silicon and / or germanium, or silicon and / or germanium, more preferably silicon. Embodiment 9: A molecular sieve according to any one of Embodiments 1 to 8, wherein at least a portion of the molecular sieve crystals has a rod-like shape. Embodiment 10: A molecular sieve according to Embodiment 9, having a length of 30 nm to 10 mm, preferably 100 nm to 1 mm, more preferably 100 nm to 500 nm, and an aspect ratio greater than 1 and 10 or less, particularly 2 to 8. Embodiment 11: A molecular sieve according to any one of Embodiments 1 to 8, wherein at least a portion of the molecular sieve crystals has a plate-like form. Embodiment 12: A molecular sieve according to Embodiment 11, having a length of 75 nm to 1 mm, preferably 75 nm to 500 nm, more preferably 100 nm to 300 nm, and a thickness of 5 nm to 60 nm, particularly 10 nm to 50 nm, and more particularly 20 nm to 30 nm. Embodiment 13: A molecular sieve according to any one of Embodiments 1 to 12, wherein the sieve is a silicate, aluminosilicate, borosilicate, or aluminoborosilicate, and the Si / X molar ratio is 5 to 300 (if Al and / or B is present), preferably 10 to 100, more preferably 15 to 75. Embodiment 14: (a) A step of preparing a synthetic mixture comprising water, a source of tetravalent element oxide (Y), a source of trivalent element oxide (X), a structural indicator (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F), and optionally a source of alkali metal elements and / or alkaline earth metal elements (M), (b) A step of heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve. (c) A step of recovering at least a portion of the molecular sieve from step (b), and (d) Optionally, process the molecular sieves recovered in step (c) to remove at least a portion of the structural indicator (Q). Includes, The structural indicator (Q) comprises at least one cation selected from the following: 1-methylimidazo[1,2-a]pyridine-1-ium cation of formula I, 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III, 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV, and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium of formula V: JPEG2026509429000021.jpg133134 A method for producing molecular sieves according to any one of Embodiments 1 to 13. Embodiment 15: The method according to Embodiment 14, wherein the structural indicator (Q) is in the form of a halide, hydroxide, or nitrate, preferably in the form of a hydroxide. Embodiment 16: The method according to Embodiment 14 or 15, wherein the tetravalent element (Y) is selected from the group consisting of silicon, titanium, zirconium, tin, germanium, and mixtures thereof, preferably the tetravalent element (Y) comprises silicon and / or germanium, more preferably the tetravalent element (Y) is silicon and / or germanium, and most preferably silicon. Embodiment 17: The method according to any one of Embodiments 14 to 16, wherein the trivalent element (X) is selected from the group consisting of aluminum, boron, iron, gallium, and mixtures thereof, preferably the trivalent element (X) comprises aluminum and / or boron, and more preferably the trivalent element (X) is aluminum and / or boron, particularly aluminum. Embodiment 18: The synthetic mixture has the following composition in terms of molar ratio: TIFF2026509429000022.tif57131 The method according to any one of embodiments 14 to 17, wherein the method is characterized by having the following: Embodiment 19: A method for converting an organic compound into a conversion product, comprising contacting the organic compound with a molecular sieve according to any one of Embodiments 1 to 13.

Claims

1. In terms of firing methods, see Table 1 below: A molecular sieve having an X-ray diffraction pattern that includes the peak shown.

2. The following equation V: (m) X ２ O ３ : YO ２ (Formula V) (In the formula, 0 ≤ m ≤ 0.1, X is a trivalent element, and Y is a tetravalent element; in particular, X comprises one or more of aluminum, boron, iron, and gallium, preferably X comprises aluminum and / or boron, or aluminum and / or boron; and Y comprises one or more of silicon, titanium, zirconium, tin, and germanium, preferably Y consists of silicon and / or germanium, or silicon and / or germanium, more preferably silicon.) A molecular sieve according to claim 1, having the molecular formula.

3. Table 2: In its synthesized form: A molecular sieve having an X-ray diffraction pattern that includes the following peaks shown.

4. The following formula VI: (q)Q: (m)X ２ O ３ :YO ２ (VI)、 (wherein 0 < q ≤ 0.7, 0 ≤ m ≤ 0.1, X is a trivalent element, Y is a tetravalent element, and Q comprises at least one cation selected from the 1-methylimidazo[1,2-a]pyridine-1-ium cation of formula I, the 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III, the 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV, and the 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium of formula V: In particular, X comprises one or more of aluminum, boron, iron, and gallium, preferably X comprises aluminum and / or boron, or aluminum and / or boron; and Y comprises one or more of silicon, titanium, zirconium, tin, and germanium, preferably Y comprises silicon and / or germanium, or silicon and / or germanium, and more preferably silicon. Molecular sieve according to claim 3 having the molecular formula

5. The molecular sieve according to any one of claims 1 to 4, wherein at least a portion of the crystals of the molecular sieve have a rod-like shape.

6. The molecular sieve according to claim 5, having a length of 30 nm to 10 mm, preferably 100 nm to 1 mm, more preferably 100 nm to 500 nm, and an aspect ratio greater than 1 and 10 or less, particularly 2 to 8.

7. The molecular sieve according to any one of claims 1 to 4, wherein at least a portion of the crystals of the molecular sieve has a plate-like form.

8. A molecular sieve according to any one of claims 1 to 7, wherein the molecular sieve is a silicate, aluminosilicate, borosilicate, or aluminoborosilicate, and has a Si / X molar ratio of 5 to 300 (in the presence of Al and / or B), preferably 10 to 100, more preferably 15 to 75.

9. (a) A step of preparing a synthetic mixture comprising water, a source of tetravalent element oxides (Y), a source of trivalent element oxides (X), a structural indicator (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F), and optionally a source of alkali metal elements and / or alkaline earth metal elements (M). (b) A step of heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve. (c) A step of recovering at least a portion of the molecular sieve from step (b), and (d) Optionally, process the molecular sieves recovered in step (c) to remove at least a portion of the structural indicator (Q). Includes, The structural indicator (Q) comprises at least one cation selected from the following: 1-methylimidazo[1,2-a]pyridine-1-ium cation of formula I, 1,2-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula II, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5-ium cation of formula III, 1,6-dimethylimidazo[1,2-a]pyridine-1-ium cation of formula IV, and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-ium of formula V: A method for producing molecular sieves according to any one of claims 1 to 8.

10. The method according to claim 9, wherein the structural indicator (Q) is in the form of a halide, hydroxide, or nitrate, preferably in the form of a hydroxide.

11. The method according to claim 9 or 10, wherein the tetravalent element (Y) is selected from the group consisting of silicon, titanium, zirconium, tin, germanium, and mixtures thereof, preferably the tetravalent element (Y) comprises silicon and / or germanium, more preferably the tetravalent element (Y) is silicon and / or germanium, and most preferably silicon.

12. The method according to any one of claims 9 to 11, wherein the trivalent element (X) is selected from the group consisting of aluminum, boron, iron, gallium, and mixtures thereof, preferably the trivalent element (X) comprises aluminum and / or boron, more preferably the trivalent element (X) is aluminum and / or boron, and particularly aluminum.

13. The synthetic mixture has the following composition in terms of molar ratio: The method according to any one of claims 9 to 12, comprising:

14. A method for converting an organic compound into a conversion product, comprising contacting the organic compound with a molecular sieve according to any one of claims 1 to 8.

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