Emm-63 aluminosilicate zeolite, synthesis and uses

Abstract

The present invention provides an aluminosilicate zeolite designated EMM-63, characterized by a unique powder XRD pattern or unique linkages; also provided are methods of making and uses thereof.

Description

[0001] Cross-references to related applications

[0002] This application claims priority and benefit to U.S. Provisional Application No. 63 / 261474, filed September 22, 2021, which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure relates to aluminosilicate zeolites, their manufacturing methods, and their uses. Background Technology

[0004] Molecular sieve materials, both natural and synthetic, can be used as adsorbents and possess catalytic properties for hydrocarbon conversion reactions. Some molecular sieves, such as zeolites, AlPO, and mesoporous materials, are ordered porous crystalline materials with well-defined crystalline structures as determined by X-ray diffraction (XRD). Some molecular sieves are ordered and produce specific, identifiable XRD patterns. Within some molecular sieve materials, numerous pores exist, interconnected by many channels or pores. Within specific molecular sieve materials, these pores and pores are of uniform size. Because the size of these pores is sufficient to accept adsorbed molecules of a certain size while rejecting larger molecules, these materials are called "molecular sieves" and are used in various industrial processes such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0005] Molecular sieves used in catalysis and adsorption include any naturally occurring or synthetic crystalline molecular sieve. Examples of these molecular sieves include macroporous zeolites, mesoporous zeolites, and microporous zeolites. These zeolites and their isotypes are classified by the International Zeolite Association (IUPAC) Structural Committee according to the rules of the IUPAC Zeolite Nomenclature Committee. According to this classification, framework-type zeolites with known structures and other crystalline microporous molecular sieves are assigned three-letter codes and described in "Atlas of Zeolite Framework Types," edited by Ch. Baerlocher, LB, et al., Elsevier, 6th edition, 2007, which is incorporated herein by reference. These zeolites and their isotypes are also described in the IZA Structural Committee's Zeolite Structure Database. Macroporous zeolites typically have at least approximately The pore sizes range from large to large, including LTL, VFI (“extra-large” 18R), MAZ, FAU, OFF, *BEA, and MOR framework zeolites. Examples of large (or extra-large) pore zeolites include mazzite, offretite, L-type zeolite, VPI-5, Y-type zeolite, X-type zeolite, ω-type zeolite, and β-type zeolite. Medium-pore zeolites typically have approximately [pore size missing]. to less than approximately The pore sizes range from small to large, and include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework zeolites. Examples of medium-pore zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, Siliceous Rock 1, and Siliceous Rock 2. Small-pore zeolites have approximately... to less than approximately Pore ​​sizes, and include, for example, framework zeolites such as CHA, RTH, ERI, KFI, LEV, SOD, and LTA. Examples of small-pore zeolites include ZK-4, ZSM-2, SAP0-34, SAP0-35, ZK-14, SAP0-42, ZK-21, ZK-22, ZK-5, ZK-20, type A zeolites, chabazite, type T zeolites, and ALPO-17.

[0006] The idealized inorganic framework structure of zeolite is a silicate framework in which all tetrahedral atoms are bonded to four next-nearest neighbor tetrahedral atoms via oxygen atoms. As used herein, the term "silicate" refers to a substance containing at least alternating silicon and oxygen atoms (i.e., -O-Si-O-Si-) and optionally other atoms, such as boron, aluminum, or other metals (e.g., transition metals like titanium, vanadium, or zinc), within the inorganic framework structure. Atoms other than silicon and oxygen in the framework silicate occupy a portion of the lattice positions that would normally be occupied by silicon atoms in a 'pure silica' framework silicate. Therefore, as used herein, the term "framework silicate" refers to an atomic lattice including any of silicates, borosilicates, gallium silicates, iron silicates, aluminosilicates, titanosilicates, zinc silicates, vanadium silicates, etc.

[0007] The framework silicate structure within a given zeolite determines the size of the pores or channels present therein. The size of these pores or channels can determine the type of process suitable for a given zeolite. Currently, the International Zeolite Association's Structure Committee has identified and recognized over 200 unique zeolite framework silicate structures, thus defining a range of pore geometries and orientations.

[0008] The framework silicates of zeolites are typically characterized by their ring size, which refers to the number of silicon atoms (or substitute atoms, as listed above) tetrahedral coordinated with oxygen atoms in the ring to define pores or channels within the zeolite. For example, an "8-membered ring" zeolite is one having pores or channels defined by eight alternating tetrahedral atoms and eight oxygen atoms in the ring. Depending on the various structural constraints present in a particular framework silicate, the pores or channels defined within a given zeolite can be symmetrical or asymmetrical.

[0009] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthetic mixture containing sources of all elements present in zeolites, such as silica sources and alumina sources. In many cases, structure-directing agents (SDAs) are also present. SDAs are compounds believed to promote the formation of molecular sieves; they are thought to act as templates around which specific molecular sieve structures can be formed, thereby promoting the formation of the desired molecular sieve. A variety of compounds have been used as structure-directing agents, including various types of quaternary ammonium cations. Typically, zeolite crystals form around the structure-directing agent, and once crystallization is complete, the structure-directing agent occupies the pores in the zeolite. Therefore, the “initial synthesized” zeolite will contain the structure-directing agent in its pores, and after crystallization, the “initial synthesized” zeolite typically undergoes processing steps, such as calcination, to remove the structure-directing agent.

[0010] Although many different zeolites have been discovered, there remains a need for new zeolites with desirable properties for gas separation and drying, organic conversion reactions, and other applications. New zeolites can contain novel endoporous structures, thus providing greater selectivity in these processes. Summary of the Invention

[0011] This disclosure relates to aluminosilicate zeolites, their manufacturing methods, and their uses.

[0012] In a first embodiment, this disclosure relates to an aluminosilicate zeolite in its initial calcined state (e.g., where at least a portion of the SDA has been removed), wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10, or 12, or 14, or 16, or preferably all of the peaks of 2θ degrees selected from Table 1:

[0013] Table 1

[0014]

[0015] In a second embodiment, this disclosure relates to an aluminosilicate zeolite in its initial synthetic form (e.g., where SDA has not yet been removed), wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10, or 12, or 14, or preferably all of the peaks at 2θ degrees selected from Table 2:

[0016] Table 2

[0017]

[0018] In a third embodiment, this disclosure relates to an aluminosilicate zeolite (whether in a pre-synthetic state, a pre-treated state (e.g., treated with acid or acid and steam), and / or a pre-calcined state) having the following structure, said structure having: (a) an orthogonal space group Pmma, and a cell size of and and (b) a 10×8×8 channel system, wherein the size of the 10-element ring hole along the c-axis is The dimensions of the 8-membered ring hole along the c-axis are And the dimensions of the individual 8-membered ring hole in the xz plane are

[0019] In a fourth embodiment, this disclosure relates to an aluminosilicate zeolite (whether in a pre-synthetic state, a pre-treated state (e.g., treated with acid or acid and steam), and / or a pre-calcined state) having a framework defined by the connection of tetrahedral (T) atoms of the unit cell in Table 3 below, wherein the tetrahedral (T) atoms are connected by bridging atoms.

[0020] Table 3

[0021]

[0022] Topologically equivalent atomic positions have the same "T-type" symbol.

[0023] Size and number of minimum rings at each angle of b T atoms (M. O'Keeffe et al., Zeolites, Vol. 19, p. 370 (1997)).

[0024] In a fifth embodiment, this disclosure relates to a method for manufacturing aluminosilicate zeolite, the method comprising the steps of: (a) preparing a synthetic mixture comprising water, a silica source, an alumina source, a potassium source, a hydroxide ion (OH) source, and tetramethylpyridine selected from formula III. Cation-directing agent (Q):

[0025]

[0026] Where n is 3; (b) heating the synthetic mixture under crystallization conditions including temperatures from 100°C to 200°C for a time sufficient to form crystals of the aluminosilicate zeolite; (c) recovering at least a portion of the aluminosilicate zeolite from step (b); and (d) optionally treating the aluminosilicate zeolite recovered in step (c) to remove at least a portion of the structure directing agent (Q).

[0027] In a sixth embodiment, the present invention relates to a method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with an aluminosilicate zeolite prepared according to the first, second, third or fourth embodiment or the method of the fifth embodiment.

[0028] These and other features and properties of this disclosure, and their advantageous applications and / or uses, will become apparent from the following detailed description. It will be understood, of course, that features described with respect to one aspect of the invention may be incorporated into other aspects of the invention. In particular, any two or more features described herein, including in the summary section, may be combined to form combinations of features not specifically described herein. Attached Figure Description

[0029] Figure 1 The powder XRD pattern of the initial calcined product of Example 1 is shown.

[0030] Figure 2 SEM images of the initial synthesized product of Example 1 are shown.

[0031] Figure 3 SEM images of the initial synthesized product of Example 3 are shown.

[0032] Figure 4 SEM images of the initial synthesized product of Example 4 are shown.

[0033] Figure 5 SEM images of the initial synthesized product of Example 5 are shown.

[0034] Figure 6 The powder XRD of the initial calcined products of Examples 2, 4 and 5 is shown.

[0035] Figure 7 The crystal structure of EMM-63, as determined by electron diffraction, is shown.

[0036] Figure 8 The powder XRD patterns of the product of Example 7 in its initial synthesized state, initial calcined state, and ammonium exchange state are shown. Detailed Implementation

[0037] This disclosure relates to aluminosilicate zeolites, their manufacturing methods, and their uses. The aluminosilicate zeolites may be designated as EMM-63 zeolite or EMM-63 material.

[0038] The aluminosilicate zeolites of this disclosure (i.e., prior to heat treatment or other treatments to remove SDA from the pores) typically contain one of the components of the synthetic mixture, SDA, within their pores. The aluminosilicate zeolites of this disclosure in which some or all of the structure-directing agent (SDA) has been removed (e.g., by heat treatment or other treatments to remove SDA from the pores) are at least partially calcined materials or "pre-calcined" materials.

[0039] In a first embodiment, this disclosure relates to an aluminosilicate zeolite in its initial calcined state (e.g., where at least a portion of the SDA has been removed), wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10, or 12, or 14, or 16, or preferably all of the peaks of 2θ degrees selected from Table 1:

[0040] Table 1

[0041]

[0042] In another embodiment, the aluminosilicate zeolite, in its initial calcined state, may have an X-ray diffraction pattern containing at least 10, 12, 14, 16, or preferably all of the 2θ-degree and d-interval values ​​selected from Table 1A, wherein the d-interval values, when converted to corresponding values ​​using Bragg's law, have a deviation based on a corresponding deviation ±0.20 2θ degrees.

[0043] Table 1A

[0044]

[0045] The XRD patterns with the XRD peaks described herein were obtained using Cu(Kα) radiation.

[0046] In one or more other embodiments, the aluminosilicate zeolite, in its initial calcined state, may have a micropore volume of 0.10 to 0.30 cc / g, or 0.12 to 0.20 cc / g, for example, 0.16 cc / g.

[0047] In one or more other embodiments, the aluminosilicate zeolite, in its initial calcined state, may have a BET surface area of ​​250 to 700 m². 2 / g, or 300 to 600m 2 / g, such as 350 to 500m 2 / g, for example 444m 2 / g.

[0048] In one or more other embodiments, the aluminosilicate zeolite, in its initial calcined state, may optionally be represented by the molecular formula of Formula I:

[0049] (m)Al2O3:SiO2 (Formula I),

[0050] Wherein 0.05 ≤ m ≤ 0.17. The oxygen atom in Formula I may be replaced by a carbon atom (e.g., in the form of CH2), which may originate from a source of components used to prepare the aluminosilicate zeolite in its initial calcined state. The oxygen atom in Formula I may also be replaced by a nitrogen atom, for example, after removal of SDA. Formula I may represent the framework of a typical aluminosilicate zeolite as defined in this disclosure in its initial calcined state, and is not intended to be the only representation of such aluminosilicate zeolite. The aluminosilicate zeolite, in its initial calcined state, may also contain SDA and / or impurities after appropriate treatment to remove SDA and impurities not described in Formula I. Furthermore, Formula I does not include protons and charge-compensating ions that may be present in the aluminosilicate zeolite in its initial calcined state.

[0051] The variable m represents the molar ratio of Al₂O₃ to SiO₂ in Equation I. For example, when m is 0.05, the molar ratio of SiO₂ to Al₂O₃ is 20 and the molar ratio of Si to Al is 10. m can vary from 0.05 to 0.17, such as at least 0.06 to at most 0.1, such as at most 0.08, for example 0.06 or 0.07. The molar ratio of Si to Al can be from 3 to 10, such as at least 5, or at least 6 and up to 9, or up to 8, for example 7 or 8.

[0052] In one or more other embodiments, the aluminosilicate zeolite, in its initial calcined state, may contain potassium ions, with a K to Al molar ratio of 0.5 to 1.0, such as 0.7 to 0.9.

[0053] In a second embodiment, this disclosure relates to an aluminosilicate zeolite, particularly an aluminosilicate zeolite as defined in the first embodiment, wherein, in its initial synthetic state (e.g., where SDA has not yet been removed), the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10, or 12, or 14, or preferably all of the 2θ-degree peaks selected from Table 2:

[0054] Table 2

[0055]

[0056] In another embodiment, the aluminosilicate zeolite, in its initial synthetic form, may have an X-ray diffraction pattern containing at least 10, 12, 14, or preferably all of the 2θ-degree and d-interval values ​​selected from Table 2A, wherein the d-interval values, when converted to corresponding values ​​using Bragg's law, have a deviation based on a corresponding deviation ±0.20 2θ degrees.

[0057] Table 2A

[0058]

[0059] The XRD patterns with the XRD peaks described herein were obtained using Cu(Kα) radiation.

[0060] In one or more other embodiments, the aluminosilicate zeolite, in its initial synthetic form, may optionally be represented by the molecular formula of Formula II:

[0061] (q)Q:(m)Al2O3:SiO2 (Formula II),

[0062] Where 0 ≤ q ≤ 0.2, 0.05 ≤ m ≤ 0.17, and Q is selected from tetramethylpyridine of formula III. cation:

[0063]

[0064] Where n is 3, for example, selected from N,2,3,5-tetramethylpyridine N,2,4,6-Tetramethylpyridine and mixtures thereof. Formula II may represent the framework of a typical aluminosilicate zeolite as defined in this disclosure in its initial synthetic form, and therefore contains a structure-directing agent (Q), and is not intended to be the only representation of such a material. The aluminosilicate zeolite, in its initial synthetic form, may contain impurities not described in Formula II. Furthermore, Formula II does not include protons and charge-compensating ions that may be present in the initial synthetic aluminosilicate zeolite.

[0065] The variable m represents the molar ratio of Al2O3 to SiO2 in Equation II. The value of variable m in Equation II is the same as the value described in Equation I in this paper.

[0066] The variable q represents the molar relationship between Q and SiO2 in Equation II. For example, when q is 0.1, the molar ratio of Q to SiO2 is 0.1. The molar ratio of Q to SiO2 can vary from 0 to 0.2, such as from 0.02 to 0.1, or for example, from 0.03 to 0.06.

[0067] In a third embodiment, this disclosure relates to an aluminosilicate zeolite, particularly an aluminosilicate zeolite as defined in the first and / or second embodiments (whether in a pre-synthetic state, a pre-treated state (e.g., treated with acid or acid and steam), and / or a pre-calcined state), having the following structure: (a) an orthorhombic space group Pmma, with a cell size of and and (b) a 10×8×8 channel system, wherein the size of the 10-element ring hole along the c-axis is The dimensions of the 8-membered ring hole along the c-axis are And the dimensions of the individual 8-membered ring hole in the xz plane are

[0068] In a fourth embodiment, this disclosure relates to an aluminosilicate zeolite, particularly an aluminosilicate zeolite as defined in the first, second and / or third embodiments (whether in a pre-synthetic state, a pre-treated state (e.g., treated with acid or acid and steam) and / or a pre-calcined state), having a framework defined by the connection of tetrahedral (T) atoms of the unit cell in Table 3 below, wherein the tetrahedral (T) atoms are connected by bridging atoms.

[0069] Table 3

[0070]

[0071] Topologically equivalent atomic positions have the same "T-type" symbol.

[0072] Size and number of minimum rings at each angle of b T atoms (M. O'Keeffe et al., Zeolites, Vol. 19, p. 370 (1997)).

[0073] The connections can be determined, for example, using the common software TOTOPOL, based on MMJ Treacy et al., “IZA Structure Committee Zeolite Structure Database” (see, for example, MMJ Treacy et al. (2004), Microporous and Mesoporous Materials, Vol. 74, pp. 121-132). The tetrahedral atoms may include one or more elements selected from B, Al, Fe, Ga, Si, Ge, Sn, Ti, and Zr, or mixtures thereof. For example, the tetrahedral atoms may be selected from B, Al, or Si, or mixtures thereof. For example, the tetrahedral atoms may contain Si or Al, or Si or Al. The bridging atoms may be selected from O, N, and C, or mixtures thereof. The bridging atoms may contain oxygen atoms or oxygen atoms (e.g., at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the bridging atoms may be oxygen). Bridging atoms C may be incorporated from various components used to manufacture zeolites, such as silica sources. Bridging atoms N may be incorporated into the zeolite after the removal of SDA.

[0074] The Si / Al molar ratio of the aluminosilicate zeolite as defined in the first, second, third and / or fourth embodiments can be 3 to 10, preferably 5 to 9.

[0075] In a fifth embodiment, this disclosure relates to a method for manufacturing aluminosilicate zeolites, particularly aluminosilicate zeolites as defined in the first, second, third, and / or fourth embodiments, the method comprising the following steps:

[0076] (a) Preparing a synthetic mixture comprising water, a silica source, an alumina source, a potassium (K) source, a hydroxide ion (OH) source, and tetramethylpyridine selected from formula III. Cation-directing agent (Q):

[0077]

[0078] Where n is 3;

[0079] (b) Heating the synthetic mixture for a time sufficient to form crystals of the aluminosilicate zeolite under crystallization conditions including temperatures from 100°C to 200°C;

[0080] (c) Recover at least a portion of the aluminosilicate zeolite from step (b); and

[0081] (d) Optionally, the aluminosilicate zeolite recovered in step (c) is treated to remove at least a portion of the structure directing agent (Q).

[0082] The structure-directing agent (Q) can be any tetramethylpyridine as defined above. Tetramethylpyridine, including at least one of the cations, such as N,2,3,4-, N,2,3,5-, or N,2,3,6-. For example, the structure-directing agent (Q) may be selected from N,2,3,5-tetramethylpyridine. N,2,4,6-Tetramethylpyridine and mixtures thereof. The structure-directing agent (Q) may be present in any suitable form, such as as a halide, like a chloride or bromide, as a hydroxide, or as a nitrate, for example, as its hydroxide. The structure-directing agent (Q) may be present in the synthetic mixture at a Q / Si molar ratio of 0.05 to 1.0, wherein the Q / Si molar ratio is, for example, at least 0.1, or at least 0.15, or at least 0.2, up to at most 0.8, or at most 0.7, or at most 0.6, for example 0.15 to 0.5, for example 0.3.

[0083] The synthetic mixture contains at least one silica source. Suitable silica sources (e.g., silicon oxide sources) include silicates, such as tetraalkyl orthosilicates like tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), and pyrolytic silica such as... (Available from Evonik) (available from Cabot) and (Available from DMS), precipitated silica such as and 340 (available from Evonik), alkali metal silicates such as potassium silicate and sodium silicate, and aqueous colloidal suspensions of silica, for example, by EIdu Pont de Nemours under the trade name Sold or sold by Evonik under the trade name For sale; preferably silicates, pyrolytic silica, precipitated silica, alkali metal silicates, colloidal silica, especially aqueous colloidal suspensions of silica.

[0084] The synthetic mixture contains at least one alumina source. Suitable alumina sources (e.g., aluminum oxide sources) include aluminum salts, especially water-soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, alkali metal aluminates such as sodium aluminate and potassium aluminate, and aluminum alkoxides such as aluminum isopropoxide, as well as hydrated alumina such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other aluminum sources include, but are not limited to, other water-soluble aluminum salts, sodium aluminate, aluminum alkoxides such as aluminum isopropoxide, or metallic aluminum such as flake aluminum. Particularly suitable alumina sources are water-soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, and alkali metal aluminates such as sodium aluminate and potassium aluminate.

[0085] Alternatively, sources containing both Si and Al elements can be used as substitutes or additions to the aforementioned Si and Al sources. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gel or dry silica-alumina powder, silica-alumina, clays such as kaolin, metakaolin, and zeolites, especially aluminosilicates, such as synthetic octahedral zeolites and ultrastable octahedral zeolites, such as ultrastable Y (USY), β-zeolite, or other macroporous to mesoporous zeolites.

[0086] The Si / Al molar ratio of the synthetic mixture can be from 1 to 50, such as 5 to 25, for example 5 to 15, for example 10.

[0087] The synthetic mixture contains at least one potassium (K) source. Suitable potassium sources include potassium hydroxide, potassium aluminate, potassium silicate, potassium salts such as KCl or KBr, or potassium nitrate, such as potassium hydroxide. The potassium may also be present in one or more of the alumina sources, such as potassium aluminate, and / or in one or more of the silica sources, such as potassium silicate. The synthetic mixture may contain the potassium source at a K / Si molar ratio of 0.05 to 1.0, wherein the K / Si molar ratio is, for example, 0.1 to 1.0, 0.15 to 0.5, or 0.3.

[0088] The synthetic mixture contains at least one hydroxide ion (OH) source. For example, the hydroxide ion may be present as a counterion of the structure directing agent (Q) and / or potassium, and / or as a counterion of an optional alkali metal or alkaline earth metal cation (M) other than potassium, and / or by using aluminum hydroxide as the Al source. Suitable hydroxide ion sources may also be selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; particularly potassium hydroxide. The synthetic mixture may contain the hydroxide ion source at an OH / Si molar ratio of 0.1 to 1.5, said OH / Si molar ratio being, for example, 0.15 to 1.2 or 0.25 to 0.8, for example, 0.6.

[0089] The synthetic mixture may optionally contain at least one alkali metal or alkaline earth metal cation (M) other than potassium. If present, M is preferably selected from sodium, lithium, rubidium, calcium, magnesium, and mixtures thereof, with sodium being preferred. The sodium source, when present, may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or sodium salts such as sodium chloride, NaBr, or sodium nitrate. The lithium source, when present, may be lithium hydroxide or lithium salts such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. The rubidium source, when present, may be rubidium hydroxide or rubidium salts such as RbCl, RbBr, RbI, or rubidium nitrate. The calcium source, when present, may be, for example, calcium hydroxide. The magnesium source, when present, may be, for example, magnesium hydroxide. The alkali metal or alkaline earth metal cation M may also be present in one or more of the alumina sources, such as sodium aluminate, and / or in one or more of the silica sources, such as sodium silicate. The synthetic mixture may contain the alkali metal or alkaline earth metal cation (M) source at an M / Si molar ratio of 0 to 1.5, wherein the M / Si molar ratio is, for example, 0 or 0.05 to 1.0 or 0.8, for example, 0. Alternatively, the synthetic mixture may not contain alkali metal or alkaline earth metal cations (M) other than potassium.

[0090] The synthetic mixture may optionally contain at least one halide ion (W) source, which may be selected from fluoride, chloride, bromide, or iodide ions. The halide ion (W) source may be any compound capable of releasing halide ions from the molecular sieve synthetic mixture. Non-limiting examples of halide ion sources include hydrogen fluoride, ammonium fluoride (NH4F), ammonium hydrogen fluoride (NH4HF2), hydrogen chloride, ammonium chloride, hydrogen bromide, ammonium bromide, hydrogen iodide, and ammonium iodide; salts containing one or more halide ions, such as metal halides, preferably wherein the metal is sodium, potassium, calcium, magnesium, strontium, or barium; ammonium halide; or tetraalkyl ammonium halide, such as tetramethylammonium halide or tetraethylammonium halide. The halide ion (W) may be present at a W / Si molar ratio of 0 to 0.2, for example, 0 to 0.1, for example, less than 0.1 or even 0. If fluoride ions are present in the synthetic mixture, the fluoride ions (F) may be present at an F / Si molar ratio of 0 to less than 0.1, for example, 0 to 0.05, or 0. Alternatively, the synthetic mixture may be free of halide ion (W) sources, particularly at least free of fluoride ion sources.

[0091] The synthesis can 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 aluminosilicate zeolite or EMM-63 material of this disclosure from previous synthesis, and may be appropriately present in the synthesis mixture in an amount from about 0.01 ppm (w / w) to about 10,000 ppm (w / w), for example from about 100 ppm (w / w) to about 5,000 ppm (w / w) of the synthesis mixture.

[0092] The synthetic mixture typically contains water, with an H2O / Si molar ratio of 1 to 100, such as 15 to 80, for example 20 to 50, or even 30. Depending on the nature of the components in the base mixture, the solvent content of the base mixture (e.g., water from a hydroxide solution, and optionally methanol and ethanol from the hydrolysis of a silica source) can be removed to achieve a desired solvent to Si molar ratio in the synthetic mixture. Suitable methods for reducing the solvent content may include evaporation under a static or flowing atmosphere such as ambient air, dry nitrogen, or dry air, or by spray drying or freeze drying. When too much water is removed during solvent removal, water can be added to the resulting mixture to achieve the desired H2O / Si molar ratio. In some instances, water removal is not necessary when the preparation has a sufficient H2O / Si molar ratio.

[0093] Carbon in the form of CH2 can be present in various component sources used to prepare the aluminosilicate zeolite of this disclosure, such as silica or alumina sources, and can be incorporated into the aluminosilicate zeolite framework as a bridging atom. Nitrogen atoms can be incorporated into the aluminosilicate zeolite framework as bridging atoms after the removal of SDA.

[0094] In one or more aspects, the solvent-adjusted (e.g., where a desired water to silica ratio is achieved) synthetic mixture may be mixed by mechanical methods such as stirring or high-shear blending to ensure proper homogenization of the base mixture, for example, using a dual asymmetric centrifugal mixer (e.g., FlackTek speedmixer) at a mixing speed of 1000 rpm to 3000 rpm (e.g., 2000 rpm).

[0095] The synthesized mixture is then subjected to crystallization conditions suitable for the formation of the aluminosilicate zeolite. The crystallization of the aluminosilicate zeolite can be carried out in a suitable reactor vessel, such as a convection oven placed at a suitable temperature. The process is carried out in a lined or stainless steel autoclave under static or stirred conditions.

[0096] The crystallization in step (b) of the method is typically carried out at a temperature of 100°C to 200°C, such as 110°C to 170°C, such as 120°C to 150°C, for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be shortened. For example, the crystallization conditions in step (b) of the method may include heating for a period of 1 to 100 days, such as 1 to 50 days, such as 1 to 30 days, such as at least 1 day or at least 5 days up to 15 or 10 days. The crystallization time can be determined by methods known in the art, for example by sampling the synthetic mixture at multiple times and determining the yield of the precipitated solid and the X-ray crystallinity. Unless otherwise indicated herein, the measured temperature is the temperature of the environment surrounding the heated material, such as the temperature of the atmosphere in which the material is heated.

[0097] Typically, the aluminosilicate zeolite is formed in solution and can be recovered by standard methods, such as centrifugation or filtration. The separated aluminosilicate zeolite can also be washed, recovered by centrifugation or filtration, and dried.

[0098] The aluminosilicate zeolite disclosed herein, when used as an adsorbent or catalyst in the conversion of organic compounds, can be at least partially dehydrated (e.g., dried). This can be accomplished by heating to a temperature ranging from 80°C to 500°C, such as 90°C to 370°C, for 30 minutes to 48 hours in an atmosphere such as air or nitrogen, and at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. Dehydration can also be carried out at room temperature simply by placing the molecular sieve in a vacuum, but this requires a longer time to obtain sufficient dehydration.

[0099] As a result of the crystallization process, the recovered product contains at least a portion of the structure-directing agent used in the synthesis within its pores. Therefore, the pre-synthesized aluminosilicate zeolite recovered from step (c) can be subjected to heat treatment or other treatments to remove some or all of the SDA incorporated into its pores during the synthesis. The heat treatment (e.g., calcination) of the pre-synthesized aluminosilicate zeolite is typically performed in a furnace in an atmosphere selected from air, nitrogen, ozone, or mixtures thereof, exposing the material to a high temperature sufficient to remove some or all of the SDA. While the heat treatment can be performed at pressures below atmospheric pressure, atmospheric pressure is preferred for convenience. The heat treatment can be carried out at temperatures up to 925°C, for example, 300°C to 700°C or 400°C to 600°C. The measured temperature is the temperature of the environment surrounding the sample. The heat treatment (e.g., calcination) can be performed in a box furnace in dry air, which has been contacted with a drying tube containing a desiccant to remove moisture from the air. The heating typically involves calcination for at least 1 minute and generally does not exceed 1 day or at most a few days. The heating can be carried out initially in a nitrogen atmosphere, and then the atmosphere can be switched to air and / or ozone.

[0100] The aluminosilicate zeolite can also undergo ion exchange treatment, for example, with aqueous ammonium salts such as ammonium nitrate, ammonium chloride, and ammonium acetate, to remove residual alkali metal cations and / or alkaline earth metal cations and replace them with protons, thereby producing an acidic molecular sieve. To the desired extent, the original cations of the initially synthesized material, such as alkali metal cations, can be replaced by ion exchange with other cations. Preferred replacement cations may include hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. The ion exchange step can be performed after the initially synthesized molecular sieve has been dried. The ion exchange step can be performed before or after the calcination step.

[0101] The aluminosilicate zeolite 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 sieve as needed.

[0102] The aluminosilicate zeolites of this disclosure, in which some or all of the SDA has been removed, can be used as adsorbents or as catalysts or catalyst supports in a wide variety of hydrocarbon conversions, such as the conversion of organic compounds into conversion products. Therefore, in the sixth embodiment, this disclosure relates to the use of the aluminosilicate zeolites described herein as adsorbents or as catalysts or catalyst supports in hydrocarbon conversions. This disclosure also relates to a method for converting organic compounds into conversion products, the method comprising contacting the organic compound with the aluminosilicate zeolite as described herein.

[0103] The aluminosilicate zeolite of this disclosure (in which some or all of SDA is removed) can be used as an adsorbent, for example, to separate at least one component from a mixture of components having different adsorption characteristics relative to the material in the vapor or liquid phase. Therefore, from a mixture of components having different adsorption characteristics relative to the aluminosilicate zeolite, said component can be partially or substantially completely separated by contacting the mixture with the aluminosilicate zeolite to selectively adsorb at least one component. For example, in the process of selectively separating one or more desired feed components from remaining feed components, said feed can be contacted with an adsorbent containing the aluminosilicate zeolite of this disclosure under effective adsorption conditions, thereby forming adsorbed products and effluent products. One or more of the desired components can be recovered from the adsorbed products or effluent products.

[0104] The aluminosilicate zeolites disclosed herein (in which some or all of the SDA is removed) can also be used as catalysts to catalyze a wide variety of organic compound conversion processes. Examples of chemical conversion processes effectively catalyzed by the aluminosilicate zeolites described herein, alone or in combination with one or more other catalytically active substances, including other crystalline catalysts, include those chemical conversion processes requiring catalysts with acid activity. Examples of organic conversion processes catalyzed by the aluminosilicate zeolites described herein include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, alkyl transfer, dealkylation, hydrodecyclization, disproportionation, oligomerization, dehydrogenation cyclization, methanol to olefins, deNOx applications, and combinations thereof. The conversion of hydrocarbon feedstocks can be carried out in any convenient mode, depending on the desired process type, such as in a fluidized bed, moving bed, or fixed bed reactor.

[0105] The aluminosilicate zeolite disclosed herein can be formulated into product compositions by combining it with other materials, such as binders and / or matrix materials that provide additional hardness to the final product. These other materials can be inert or catalytically active.

[0106] For example, it may be desirable to combine the aluminosilicate zeolite of this disclosure with another material that is resistant to the temperatures and other conditions applied during use. Such materials include synthetic or naturally occurring zeolites and inorganic materials such as clay, silica, and / or metal oxides such as alumina, and mixtures thereof. The metal oxides may be naturally occurring or in the form of a gel-like precipitate or gel comprising a mixture of silica and metal oxides. The use of resistant materials in conjunction with the aluminosilicate zeolite of this disclosure, i.e., in combination with or in the presence of the zeolite in its initial state during the synthesis of the crystalline active aluminosilicate zeolite, tends to alter the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive resistant materials are suitable as diluents to control the conversion in a given process, enabling the product to be obtained in an economical and orderly manner without the need for other means of controlling the reaction rate. These materials may be incorporated into naturally occurring clays, such as bentonite and kaolin, to improve the crushing strength of the product under commercial operating conditions. The inactive resistant materials, i.e., clays, oxides, etc., act as a binder for the catalyst. Catalysts with good crushing strength can be beneficial because, in commercial applications, it is desirable to prevent the catalyst from decomposing into powdery material.

[0107] Naturally occurring clays that can be used include the montmorillonite and kaolinite families, which include sub-bentonite, and other kaolinites commonly known as Dixie, McNamee, Georgia, and Florida clays, or whose main mineral components are halloysite, kaolinite, dickite, perlite, or vermicular clay. Such clays can be used in their original, unprocessed state or after calcination, acid treatment, or chemical modification. Binders that can be used in combination with the aluminosilicate zeolites of this disclosure also include inorganic oxides selected from silica, zirconium oxide, titanium dioxide, magnesium oxide, beryllium oxide, aluminum oxide, yttrium oxide, gallium oxide, zinc oxide, and mixtures thereof.

[0108] In addition to the aforementioned materials, the aluminosilicate zeolite disclosed herein can also be combined with porous matrix materials such as silica-alumina, silica-magnesium oxide, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium dioxide, and ternary compositions such as silica-alumina-thorium oxide, silica-alumina-zirconia, silica-alumina-magnesium oxide, and silica-magnesium oxide-zirconia.

[0109] These binder materials are resistant to the temperatures and other conditions, such as mechanical abrasion, encountered in various hydrocarbon separation processes. Therefore, the aluminosilicate zeolites of this disclosure can be used in the form of extrusions along with binders. They are typically combined by forming pellets, spheres, or extrusions. The extrusions are typically formed as follows: the molecular sieve is extruded, optionally in the presence of a binder, and the resulting extrusion is dried and calcined. Further processing, such as steam treatment and / or ion exchange, can be performed as needed. The molecular sieve may optionally be combined with a binder having a surface area of ​​at least 100 m² / g, for example at least 200 m² / g, optionally at least 300 m² / g.

[0110] The relative proportion of aluminosilicate zeolite to the inorganic oxide matrix can vary widely, wherein the aluminosilicate zeolite content ranges from about 1 wt% to about 100 wt%, and more generally, particularly when the composite is prepared in the form of an extrusion, the content ranges from about 2 wt% to about 95 wt%, optionally from about 20 wt% to about 90 wt%.

[0111] The aluminosilicate zeolite disclosed herein can also be used in close combination with a hydrogenating component intended to perform a hydrogenation-dehydrogenation function, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium. Such a hydrogenating component can be incorporated into the composition by one or more of the following processes: co-crystallization; exchange into the composition until a Group IIIA element, such as aluminum, is present in the structure; or physical close mixing with it. Such a component can also be impregnated into or onto the aluminosilicate zeolite, for example, by treating the molecular sieve with ions containing a hydride metal. For example, in the case of platinum, suitable platinum compounds for this purpose include chloroplatinic acid, platinum(II) chloride, and various compounds containing platinumamine complexes. Combinations of metals and their introduction methods can also be used.

[0112] Those skilled in the art will understand that the aluminosilicate zeolites of this disclosure may contain impurities such as amorphous materials, unit cells with different topologies (e.g., quartz or molecular sieves of different framework types, which 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 types of molecular sieves or zeolites that coexist with the aluminosilicate zeolites of this disclosure are, for example, ZSM-12, mordenite, cristobalite, quartz, L-type zeolite, potassium zeolite, barium zeolite, and / or magnesium alkali zeolite. The aluminosilicate zeolites of this disclosure are preferably substantially free of impurities. As used herein, the term "substantially free of impurities" (or alternatively, "substantially pure") means that the aluminosilicate zeolite contains a small proportion (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., less than 0.5 wt% or 0.1 wt%) of such impurities, the weight percentage (wt%) being based on the combined weight of the impurities and the pure aluminosilicate zeolite. The amount of impurities can be suitably determined by powder XRD, rotating electron diffraction, and / or SEM / TEM (e.g., different crystal morphologies).

[0113] The aluminosilicate zeolites described herein are substantially crystalline. As used herein, the term "crystalline" refers to the crystalline solid form of a material, including, but not limited to, single-component or multi-component crystalline forms, such as solvates, hydrates, and eutectics. Crystallinity can mean having a regular and / or ordered molecular arrangement and a distinguishable crystal lattice. For example, aluminosilicate zeolites can have different water or solvent contents. Different crystal lattices can be identified by solid-state characterization methods, such as by XRD (e.g., powder XRD). Other characterization methods known to those skilled in the art can further aid in identifying crystal forms and in determining stability and solvent / water content. As used herein, the term "substantially crystalline" means that the majority (greater than 50 wt%) of the sample weight of the described material is crystalline, while the remainder of the sample is in a non-crystalline form. In one or more aspects, the substantially crystalline sample has a crystallinity of at least 95% (e.g., 5% amorphous form), at least 96% (e.g., 4% amorphous form), at least 97% (e.g., 3% amorphous form), at least 98% (e.g., about 2% amorphous form), at least 99% (e.g., 1% amorphous form), and 100% (e.g., 0% amorphous form).

[0114] Various aspects of this disclosure are described in more detail through specific embodiments. The following embodiments are provided for illustrative purposes and are not intended to limit the disclosure in any way. Those skilled in the art will readily recognize that various parameters can be changed or modified to produce substantially the same results.

[0115] Example

[0116] The invention is further described below, but its scope is not limited.

[0117] In these embodiments, X-ray diffraction (XRD) patterns of the pre-synthetic and pre-calcined materials were recorded in continuous mode within a 2θ range of 4 to 36 degrees using Cu Kα radiation, Bragg-Bentano geometry, and a Vantec 500 detector on an X-ray powder diffractometer (Bruker DaVinci D8 Discovery instrument). The interplanar spacing d-spacing is calculated in angstroms, and the relative intensity I / Io of the spectral lines is the ratio of the peak intensity to the intensity of the strongest spectral line exceeding the background. These intensities are not corrected for Lorentz and polarization effects. The positions of the diffraction peaks in 2θ, and the relative peak-plane intensities I / I(o) of the spectral lines, where Io is the intensity of the strongest spectral line exceeding the background, were determined using the MDI Jade peak search algorithm. It should be understood that diffraction data listed as a single spectral line may consist of multiple overlapping spectral lines, which, under certain conditions such as differences in crystallographic variations, may appear as separated or partially separated spectral lines. Typically, crystallographic variations can include minute changes in cell parameters and / or crystal symmetry, but the framework connectivity remains unchanged. These minute effects, including variations in relative intensity, can also occur due to differences in cation content, framework composition, the nature and extent of pore filling, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0118] Scanning electron microscopy (SEM) images of the initially synthesized material were obtained using a Hitachi 4800 scanning electron microscope. The SEM images were used to help assess product purity. The presence of distinctly different crystal morphologies in the SEM images can indicate impurities present in other crystalline forms. Such approximate analysis is particularly useful in identifying the formation of relatively small amounts of crystalline impurities that may not be identifiable on the product's XRD pattern.

[0119] The following measurements were performed on the samples that underwent ion exchange and calcination. The procedure for each sample that underwent ion exchange and calcination was as follows: the initial sample was washed twice with 1M ammonium nitrate solution and then calcined at 500°C for 16 hours.

[0120] The total BET surface area (SBET) of the material was determined by the BET method described in S. Brunauer et al., J. Am. Chem. Soc., 1938, Vol. 60, 309, using nitrogen adsorption-desorption at liquid nitrogen temperature, which is incorporated herein by reference.

[0121] The micropore volume (Vmicro) of the material can be determined using methods known in the relevant field. For example, the micropore volume of the material can be measured by nitrogen physisorption and the data can be analyzed by the t-plot method, which is described in Lippens, BC et al., Studies on pore system in catalysts: V. The t method, J. Catal., Vol. 4, 319 (1965), which describes the micropore volume method and is incorporated herein by reference.

[0122] The α value is a measure of the catalytic cracking activity and is described in U.S. Patent No. 3,354,078 and the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each of which is incorporated herein by reference. The experimental conditions used in the tests described herein included a constant temperature of 538 °C and variable flow rates as detailed in the Journal of Catalysis, Vol. 61, p. 395.

[0123] The molar ratios and conditions used in the synthesis of Examples 1-9, as well as the products generated, are detailed below and summarized in Table 4.

[0124] Example 1: Using N,2,3,5-tetramethylpyridine in the absence of seed crystals Synthesis performed

[0125] Starting with a synthetic mixture having the following composition in molar ratios: Si / Al = 10, H₂O / Si = 30, Q / Si = 0.30, OH / Si = 0.60, K / Si = 0.30, using N,2,3,5-tetramethylpyridine. EMM-63 was first observed as a structure-directing agent (Q) (in hydroxide form, 17.5 wt% solution) during a 28-day synthesis at 120 °C in a tumbling 1.5 mL stainless steel reactor. Ludox LS-30 (30 wt% colloidal silica suspension) was used as the Si source, aluminum hydroxide (82.6 wt% solid Al(OH)3, balance water) as the Al source, and KOH (17.5 wt% solution) as the K source.

[0126] The product was separated by centrifugation, resuspended in deionized water, and then centrifuged again. This process was repeated three times, and the product was then dried at room temperature. The initially synthesized material was then calcined to 600°C in a box furnace using the following procedure: The sample was exposed to flowing nitrogen at room temperature for two hours, and then, while maintaining the nitrogen flow, the temperature was increased from room temperature to 400°C over two hours. The temperature was then held at 400°C for 15 minutes, and then the atmosphere was switched from flowing nitrogen to flowing dry air. The temperature was then increased from 400°C to 600°C over one hour. The temperature was held at 600°C for two hours, and then the box furnace was allowed to cool.

[0127] XRD analysis of the pre-synthesized and pre-calcined materials showed that the materials had unique powder XRD patterns that could not be matched with any known zeolite, and were named the pure pre-synthesized MM-63 product and the pre-calcined EMM-63 product. Figure 1 The powder XRD of the material in its initial calcined state is shown. Figure 2 The SEM image of the initially synthesized product is shown.

[0128] Example 2: Using N,2,3,5-tetramethylpyridine in the absence of seed crystals Medium-scale synthesis

[0129] This example is a medium-scale reproduction of Example 1, synthesized in a 23 mL steel Parr reactor using 1.20 g of SiO2. After heating at 120 °C for 13 days, the product was identified by XRD pattern, yielding pure EMM-63 in a yield of 0.72 g.

[0130] Example 3: Using N,2,3,5-tetramethylpyridine Larger-scale synthesis with seed crystals

[0131] This example is a larger-scale reproduction of Examples 1 and 2, and the synthesis was carried out in a 125 mL steel Parr reactor with 11.6 g of SiO2 in the presence of seed crystals.

[0132] 40.9 g of water and 101.5 g of N,2,3,5-tetramethylpyridine as structure directing agent (Q) were mixed. (In hydroxide form, 17.5 wt% solution) Mix. Then, add 76.5 g of Ludox LS-30 (30 wt% colloidal silica suspension), 37.1 g of KOH (17.5 wt%), 3.65 g of aluminum hydroxide (82.6 wt% solid Al(OH)3, the remainder being water) and 0.23 g of seed crystals (EMM-63 prepared according to Example 2) in sequence, and stir the resulting mixture to form a reaction mixture. Divide the reaction mixture in half and pack one half into a Teflon liner.

[0133] After heating at 120°C for 9 days, the product was separated by centrifugation, resuspended in deionized water, and then centrifuged again. This process was repeated three times, and the product was then dried at 90°C. The initially synthesized material was then calcined according to the procedure in Example 1.

[0134] The product was identified by its XRD pattern as pure EMM-63, with a yield of 5.3 grams. Figure 3 SEM images of the initially synthesized product are shown. Elemental analysis of the initially calcined product by inductively coupled plasma (ICP) showed that the Si / Al atomic ratio of the material was 7.8 and the K / Al atomic ratio was 0.89.

[0135] Examples 4-5: Using N,2,3,5-tetramethylpyridine Synthesis of seed crystals at different temperatures

[0136] These examples were carried out under the same conditions as Example 2, but at 135°C and 150°C instead of 120°C, and in the presence of 0.23 g of seed crystals (EMM-63 prepared according to Example 3) added to the synthetic mixture. After heating at 135°C and 150°C for 7 days, respectively, the products were identified by XRD patterns, yielding pure EMM-63 products in yields of 0.72 g and 0.79 g, respectively. Figure 4 and Figure 5 The SEM images of the corresponding initial synthesized products are shown.

[0137] Figure 6 The powder XRD patterns of the initial synthesized materials obtained at 135°C and 150°C in Examples 4 and 5, respectively, are shown in comparison with those of the initial synthesized material obtained at 120°C in Example 2. This illustrates the effect of synthesis temperature on the width of the powder patterns of the products obtained at 120°C, 135°C, and 150°C: as the temperature increases, the crystal thickness increases, and the patterns become sharper.

[0138] Tables 5 and 6 below show the peak and intensity lists of the EMM-63 products in the initial synthesized and initial calcined states of Example 5, respectively. The powder diffraction data of the initial calcined EMM-63 product can be indexed using the orthogonal space group Pmma, where the cell size of Pmma is... and The skeleton structure has a 10×8×8 channel system. The dimensions of the 10-element ring hole along the c-axis are... The dimensions of the 8-membered ring hole along the c-axis are A single 8-membered ring hole in the xz plane also has The size. Figure 7 The crystal structure of EMM-63, as determined by electron diffraction, is shown.

[0139] Thermogravimetric analysis (TGA) was performed on the initially synthesized EMM-63 product of Example 5 by heating it in air from room temperature to 800°C. The total weight loss was 11.1 wt%. Up to 200°C, there was a loss of 3.8 wt%, which could be attributed to water. Above 250°C, there was a loss of 7.3 wt%, which could be attributed to the loss of organic SDA.

[0140] Examples 6-7: Using N,2,4,6-tetramethylpyridine Synthesis of seed crystals at different temperatures

[0141] These examples were carried out under the same conditions as Examples 4-5, at 135°C and 150°C respectively, except that N,2,4,6-tetramethylpyridine was used. (In hydroxide form, 17.5 wt% solution) instead of N,2,3,5-tetramethylpyridine As a structure-directing agent (Q), pure EMM-63 products were obtained by XRD analysis after heating at 135℃ and 150℃ for 7 days, respectively.

[0142] The initially synthesized EMM-63 material of Example 7 was calcined according to the procedure defined in Example 1, and ammonium ion exchange was performed with 1M ammonium nitrate solution in an intermittent system. Then, it was calcined again at 500°C for 16 hours to convert the material into an acidic form. Figure 8 The powder XRD patterns of the EMM-63 product in its initial synthesized state, initial calcined state, and ammonium exchange state were compared.

[0143] Example 8: Using N,2,4,6-tetramethylpyridine Synthesis with potassium aluminate

[0144] This example was conducted under the same conditions and molar ratio as Example 6, except that potassium aluminate (11.2 wt%) was used instead of aluminum hydroxide as the aluminum source. After heating at 135°C for 7 days, the product was identified by XRD pattern, yielding pure EMM-63.

[0145] Example 9: Using N,2,4,6-tetramethylpyridine Larger-scale synthesis with potassium aluminate

[0146] This example is a larger-scale reproduction of Example 8, and the synthesis was carried out in a 125 mL steel Parr reactor. After heating at 135 °C for 7 days, the product was identified by XRD pattern, yielding pure EMM-63.

[0147] The initially synthesized EMM-63 material was calcined according to the procedure defined in Example 1, and ammonium ion exchange was performed with a 1M ammonium nitrate solution in an intermittent system. Then, it was calcined again at 500°C for 16 hours to convert the material into an acidic form.

[0148] The BET surface area (SBET) of the EMM-63 material in its initial calcined and ammonium-exchange forms is 444 m² / g, its micropore volume (Vmicro) is 0.16 cc / g, and its α value is 48. The adsorption capacities of n-hexane, 2,3-dimethylbutane (2,3-DMB), and mesitylene were determined for the ion-exchange and calcined material. The material was placed under a nitrogen flow, and the hydrocarbons were introduced through a sprayer to saturate the nitrogen flow, and the adsorption capacities of the hydrocarbons were determined. Each hydrocarbon was adsorbed at different temperatures: n-hexane was adsorbed at 90°C, 2,3-DMB at 120°C, and mesitylene at 100°C. The adsorption capacities were 46.0 mg / g for n-hexane, 47.3 mg / g for 2,3-DMB, and 16.8 mg / g for mesitylene.

[0149] Table 4

[0150]

[0151]

[0152] *N,2,3,5-TMPOH=N,2,3,5-Tetramethylpyridine Hydroxide, N,2,4,6-TMPOH = N,2,4,6-Tetramethylpyridine hydroxide.

[0153] Table 5

[0154]

[0155]

[0156]

[0157] Table 6

[0158]

[0159]

[0160]

[0161] While the present invention has been described and illustrated with reference to specific embodiments, those skilled in the art will appreciate that the invention itself relates to many different variations, modifications, and alterations not specifically described herein. It will also be apparent to those skilled in the art that when lower and upper limits are listed herein, a range from any lower limit to any upper limit is considered. Furthermore, all values ​​within the specific embodiments herein are modified with "about" and experimental errors and variations that will be expected by those skilled in the art.

[0162] In the foregoing description, where integers or elements have known, obvious, or foreseeable equivalents, such equivalents are incorporated herein as if individually stated. The true scope of the invention should be determined with reference to the claims, and this true scope should be interpreted to include any such equivalents. The reader will also appreciate that integers or features of the invention described as preferred, advantageous, convenient, etc., are optional and do not limit the scope of the independent claims. Furthermore, it should be understood that such optional integers or features, while potentially beneficial in some embodiments of the invention, may be undesirable in others and therefore may not be present.

[0163] Additionally or alternatively, the present invention relates to:

[0164] Implementation Method 1: An aluminosilicate zeolite, in its initial calcined state, wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10 peaks selected from Table 1 or Table 1A.

[0165] Implementation Method 2: According to the aluminosilicate zeolite of Implementation Method 1, in its initial calcined state, the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 12, preferably at least 14, more preferably at least 16, and most preferably all of the peaks selected from Table 1 or Table 1A.

[0166] Embodiment 3: The aluminosilicate zeolite according to Embodiment 1 or 2 has the molecular formula of Formula I:

[0167] (m)Al2O3:SiO2 (Formula I),

[0168] Where 0.05≤m≤0.17.

[0169] Implementation Method 4: An aluminosilicate zeolite, in its initial synthetic state, wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10 peaks selected from Table 2 or Table 2A.

[0170] Implementation Method 5: According to the aluminosilicate zeolite of Implementation Method 4, in its initial synthesis state, the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 12, preferably at least 14, more preferably all of the peaks selected from Table 2 or Table 2A.

[0171] Embodiment 6: The aluminosilicate zeolite according to Embodiment 4 or 5 has the molecular formula of Formula II:

[0172] (q)Q:(m)Al2O3:SiO2 (Formula II),

[0173] Where 0 ≤ q ≤ 0.2, 0.05 ≤ m ≤ 0.17, and Q is selected from tetramethylpyridine of formula III. cation:

[0174]

[0175] Where n is 3; preferably, Q is selected from N,2,3,5-tetramethylpyridine. N,2,4,6-Tetramethylpyridine and its mixtures.

[0176] Embodiment 7: An aluminosilicate zeolite according to any one of Embodiments 1 to 6, having a framework defined by the connection of tetrahedral (T) atoms of the unit cell in Table 3, wherein the tetrahedral (T) atoms are connected by bridging atoms.

[0177] Embodiment 8: The aluminosilicate zeolite according to any one of Embodiments 1 to 7 has the following structure, wherein the structure has: (a) an orthorhombic space group Pmma and a cell size of and and (b) a 10×8×8 channel system, wherein the size of the 10-element ring hole along the c-axis is The dimensions of the 8-membered ring hole along the c-axis are And the dimensions of the individual 8-membered ring hole in the xz plane are

[0178] Embodiment 9: The aluminosilicate zeolite according to any one of Embodiments 1 to 8 has a Si / Al molar ratio of 3 to 10, preferably 5 to 9.

[0179] Embodiment 10: The aluminosilicate zeolite according to any one of Embodiments 1 to 3 and 7 to 9 has a micropore volume of 0.10 to 0.30 cc / g, preferably 0.12 to 0.20 cc / g, and / or a BET surface area of ​​250 to 700 m2 / g, or 300 to 600 m2 / g, for example 350 to 500 m2 / g.

[0180] Embodiment 11: A method for manufacturing aluminosilicate zeolite according to any one of Embodiments 1 to 9, the method comprising:

[0181] (a) Preparing a synthetic mixture comprising water, a silica source, an alumina source, a potassium source, a hydroxide ion (OH) source, and tetramethylpyridine selected from formula III. Cation-directing agent (Q):

[0182]

[0183] Where n is 3;

[0184] (b) Heating the synthetic mixture for a time sufficient to form crystals of the aluminosilicate zeolite under crystallization conditions including temperatures from 100°C to 200°C;

[0185] (c) Recover at least a portion of the aluminosilicate zeolite from step (b); and

[0186] (d) Optionally, the aluminosilicate zeolite recovered in step (c) is treated to remove at least a portion of the structure directing agent (Q).

[0187] Embodiment 12: The method according to Embodiment 11, wherein the structure directing agent (Q) is selected from N,2,3,5-tetramethylpyridine. N,2,4,6-Tetramethylpyridine and mixtures thereof; in particular, the structure-directing agent (Q) therein is in its hydroxide form.

[0188] Embodiment 13: The method according to Embodiment 11 or 12, wherein the synthetic mixture has the following composition according to the molar ratio:

[0189] Mole ratio Normal range Preferred range More preferred range Si / Al 1-50 5-25 5-15 Q / Si 0.05-1.0 0.1-0.8 0.15-0.5 K / Si 0.05-1.0 0.1-1.0 0.15-0.5 OH / Si 0.1-1.5 0.15-1.2 0.25-0.8 <![CDATA[H2O / Si]]> 1-100 15-80 20-50

[0190] Embodiment 14: A method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with an aluminosilicate zeolite according to any one of Embodiments 1 to 10.

Claims

1. An aluminosilicate zeolite named EMM-63, in its initial calcined state, wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains at least 10 peaks selected from Table 1: Table 1 。 2. The aluminosilicate zeolite according to claim 1, in its initial calcined state, wherein the X-ray diffraction pattern of the aluminosilicate zeolite contains all the peaks selected from Table 1.

3. The aluminosilicate zeolite according to claim 1, having the molecular formula of formula I: (m)Al2O3:SiO2 (Formula I), Where 0.05≤m≤0.

17.

4. An aluminosilicate zeolite named EMM-63, in its initial synthetic form, has an X-ray diffraction pattern containing at least 10 peaks selected from Table 2: Table 2 。 5. The aluminosilicate zeolite according to claim 4, wherein in its initial synthetic state, the X-ray diffraction pattern of the aluminosilicate zeolite contains all the peaks selected from Table 2.

6. The aluminosilicate zeolite according to claim 4, having the molecular formula of formula II: (q)Q :(m)Al2O3:SiO2 (Formula II), Where 0 ≤ q ≤ 0.2, 0.05 ≤ m ≤ 0.17, and Q is selected from N,2,3,5-tetramethylpyridine. N,2,4,6-Tetramethylpyridine and its mixtures.

7. The aluminosilicate zeolite according to any one of claims 1 to 6, having a framework defined by the connection of tetrahedral (T) atoms in the unit cell as shown in Table 3 below, wherein the tetrahedral (T) atoms are connected by bridging atoms: Table 3 Topologically equivalent atomic positions have the same "T-type" notation. The size and number of the smallest rings at each angle of the bT atom.

8. The aluminosilicate zeolite according to any one of claims 1 to 6, having the following structure, said structure having: (a) an orthogonal space group Pmma, The cell size is a = 22.1 0.20 Å, b = 7.4 0.20 Å and c = 11.8 0.20 Å, and (b) 10 8 An 8-channel system, wherein the 10-membered annular hole along the c-axis has (5.2) 0.20 Å) (4.9 The 8-membered ring hole along the c-axis has a size of 0.20 Å and a diameter of (4.7 Å). 0.20 Å) (3.1 The size is 0.20 Å, and the individual 8-membered ring aperture in the xz plane has a size of (4.7 Å). 0.20 Å) (3.1 The size is 0.20 Å.

9. The aluminosilicate zeolite according to any one of claims 1 to 6, wherein the Si / Al molar ratio is 3 to 10.

10. A method for manufacturing aluminosilicate zeolite according to any one of claims 1 to 6, the method comprising: (a) Preparing a synthetic mixture comprising water, a silica source, an alumina source, a potassium source, a hydroxide ion (OH) source, and a structure directing agent (Q) selected from N,2,3,5-tetramethylpyridine. N,2,4,6-Tetramethylpyridine and its mixtures; (b) Heating the synthetic mixture for a time sufficient to form crystals of the aluminosilicate zeolite under crystallization conditions including temperatures from 100°C to 200°C; (c) Recover at least a portion of the aluminosilicate zeolite from step (b); and (d) Optionally, the aluminosilicate zeolite recovered in step (c) is treated to remove at least a portion of the structure directing agent (Q).

11. The method of claim 10, wherein the structure directing agent (Q) is in its hydroxide form.

12. The method of claim 10, wherein the synthetic mixture has the following composition according to the molar ratio: 。 13. The method of claim 10, wherein the synthetic mixture has the following composition according to the molar ratio: 。 14. The method of claim 10, wherein the synthetic mixture has the following composition according to the molar ratio: 。 15. A method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with an aluminosilicate zeolite according to any one of claims 1 to 6.

Images