1-methyl-6,7-dihydro-5h-cyclopenta[b]pyridine-1-ium cations as structure directing agents for the preparation of zeolites and zeolites obtained thereby

Abstract

The present disclosure relates to the use of 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-oxonium cations as structure directing agents (SDAs) for the preparation of zeolites. The present disclosure also relates to the compositions of matter known as EMM-64 and EMM-65 obtainable by the use of said SDAs, to methods for their preparation and to their use. The present disclosure also relates to methods for the preparation of silicoaluminate molecular sieves of RTH framework type using said SDAs, to silicoaluminate molecular sieves of RTH framework type obtainable by said methods, and to their use.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority and interest in U.S. Provisional Application No. 63 / 212205, filed June 18, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the use of 1-methyl-6,7-dihydro-5H-cyclopentadienyl[b]pyridine-1-onium cation as a structure-directing agent (SDA) in the preparation of zeolites. This disclosure also relates to material compositions known as EMM-64 and EMM-65 that can be obtained using said SDA, methods for their preparation, and uses thereof. This disclosure further relates to a method for manufacturing RTH framework-type aluminosilicate molecular sieves using said SDA, RTH materials that can be obtained by said method, and uses thereof. Background of the Invention

[0005] Both natural and synthetic molecular sieve materials can be used as adsorbents and exhibit catalytic properties in hydrocarbon conversion reactions. Some molecular sieves, such as zeolites, AlPOs, and mesoporous materials, are ordered porous crystalline materials with well-defined crystalline structures determined by X-ray diffraction (XRD). Some molecular sieves are ordered and produce specific, identifiable XRD patterns. Numerous cavities can exist within some molecular sieve materials, interconnected by many channels or pores. In certain zeolite materials, these cavities and pores are uniformly sized. Because the size of these pores allows for the adsorption of molecules of a specific size while simultaneously blocking larger molecules, these materials are called "molecular sieves" and are used in various industrial processes such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0006] Molecular sieves that can be used in catalysis and adsorption include any natural 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 Structure Commission of the International Zeolite Association according to the IUPAC Commission's rules on zeolite nomenclature. According to this classification, framework-type zeolites and other crystalline microporous molecular sieves with established structures are assigned three-letter codes and described in "Atlas of Zeolite Framework Types," eds. Ch. Baerlocher, L.B. McCusker, and D. H. Holson, Elsevier, 6th edition, 2007, which is hereby cited and incorporated herein by reference. These zeolites and their isotypes are also described at http: / / america.iza-structure.org / IZA-SC / ftc_table.php. Macroporous zeolites typically have at least approximately The pore sizes include LTL, VFI, MAZ, FAU, OFF, *BEA, and MOR framework types of zeolites. Examples of macroporous zeolites include mazzite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X, ω, and β. Intermediate-pore zeolites typically have approximately [pore size missing]. to less than approximately The pore sizes include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework-type zeolites. Examples of intermediate-pore-size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, Silicalite 1, and Silicalite 2. Small-pore-size zeolites have approximately... to less than approximately Pore ​​sizes include, for example, zeolites with frameworks 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, zeolite A, chabazite, zeolite T, and ALPO-17.

[0007] The ideal inorganic framework structure for zeolites is a silicate framework in which all tetrahedral atoms are bonded by oxygen atoms to four nearest-nearest tetrahedral atoms. As used herein, the term "silicate" refers to a substance containing at least alternating bonds of silicon and oxygen atoms (i.e., -O-Si-O-Si-), and optionally includes other atoms within the inorganic framework structure, including atoms such as boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc). Atoms different from silicon and oxygen occupy a portion of the lattice sites in the framework silicate, with the remaining sites occupied by silicon atoms in the "all-silica" framework silicate. Therefore, as used herein, the term "framework silicate" refers to an atomic lattice comprising any one of silicates, borosilicates, gallium silicates, iron silicates, aluminosilicates, titanosilicates, zinc silicates, vanadium silicates, etc.

[0008] The structure of the framework silicate within a given zeolite determines the size of the pores or channels present therein. The size of the pores or channels can determine the type of process suitable for a given zeolite. Currently, more than 200 unique zeolite framework silicate structures are known and confirmed by the Structure Commission of the International Zeolite Association, thus defining the range of pore geometry and orientation.

[0009] The framework silicates of zeolites are typically characterized by their ring size, which refers to the number of silicon atoms (or alternative atoms, such as those listed above) tetrahedral coordinated with oxygen atoms in the rings, thus defining the pores or channels within the zeolite. For example, "8-ring" zeolites are those with pores or channels defined by eight alternating tetrahedral atoms and eight oxygen atoms in the rings. The pores or channels defined within a given zeolite can be symmetric or asymmetric, depending on the different structural constraints present in the particular framework silicate.

[0010] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthetic mixture containing all the elemental sources present in the zeolite, such as silica and alumina sources. In many cases, structure-directing agents (SDAs) are also present. SDAs are compounds believed to promote the formation of molecular sieves and are considered to act as templates around which certain molecular sieve structures can form, thereby promoting the formation of the desired molecular sieve. Many compounds have been used as structure-directing agents, including various types of quaternary ammonium cations. Typically, once crystallization is complete, zeolite crystals form around the structure-directing agent, which occupies the pores within the zeolite. Therefore, "as-synthesized" zeolite contains the structure-directing agent within its pores, and after crystallization, "as-synthesized" zeolite is usually subjected to processing steps such as calcination to remove the structure-directing agent.

[0011] For example, RTH-based zeolites were first prepared as borosilicates in the presence of 1,2,2,6,6-pentamethylpiperidine as an SDA, denoted as RUB-13 (S. Vortmann et al., Microporous Materials, 4, 111-121 (1995)). WO2001 / 044109 describes the preparation of aluminosilicate RTHs using N-ethyl-N-methyl-5,7,7-trimethyl-2-aza-onium bicyclo[4.1.1]nonane cations as SDAs, denoted as SSZ-50. Aluminosilicate RTHs have also been prepared using 2,6-methyl-N-methylpyridinium cations as SDAs (H. Xu et al., J. Mater. Chem. A, 6, 8705-8711 (2018)). An ITE-RTH structural intermediate, denoted as SSZ-36, has also been reported (P. Wagner et al., J. Am. Chem. Soc., 122, 263-273 (2000)). RTH framework-type molecular sieves have large cages with an 8x8 channel system.

[0012] It is important to identify novel structure-directing agents and more efficient methods for synthesizing molecular sieves, thereby facilitating the preparation of novel molecular sieves and / or reducing the cost of manufacturing known zeolites. Although many different crystalline molecular sieves have been discovered, there remains a need for novel molecular sieves with the desired properties for gas separation and drying, organic conversion reactions, and other applications. Novel molecular sieves can contain novel internal pore structures and provide improved selectivity in these processes.

[0013] Overview

[0014] In one aspect, this disclosure relates to the use of the 1-methyl-6,7-dihydro-5H-cyclopentadienyl[b]pyridine-1-onium cation of Formula I as a structure-directing agent (SDA) in the preparation of zeolites:

[0015]

[0016] In a second aspect, this disclosure relates to EMM-64, which is a crystalline material in calcined form (e.g., in which at least a portion of the SDA has been removed) and in its original form (e.g., in which the SDA has not been removed), and to a method for preparing the material using a 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I as the SDA, and its use.

[0017] In a third aspect, this disclosure relates to EMM-65, which is a crystalline material in calcined form (e.g., in which at least a portion of the SDA has been removed) and in its original form (e.g., in which the SDA has not been removed), and to a method for preparing the material using the 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I as the SDA, and its use.

[0018] In a fourth aspect, this disclosure relates to a method for manufacturing RTH-framework type aluminosilicate molecular sieves using the 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I as SDA, and the RTH-framework type aluminosilicate molecular sieves that can be obtained by said method, and their uses.

[0019] In a fifth aspect, this disclosure relates to an RTH framework type of aluminosilicate molecular sieve having a 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I within its pore structure.

[0020] In a sixth aspect, this disclosure relates to an RTH framework type of aluminosilicate molecular sieve having a Si / Al molar ratio of less than 10.

[0021] These and other features and advantages disclosed herein, and their advantageous applications and / or uses, will become apparent from the following detailed description. It should 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 in this specification (including in the overview section) may be combined to form a combination of features not specifically described herein.

[0022] Attached Figure Description

[0023] Figure 1 Showing the powder XRD patterns of the original and calcined products of Example 2.01.

[0024] Figure 2 This shows an SEM image of the original product prepared in Example 2.01.

[0025] Figure 3This shows an SEM image of the original product prepared in Example 2.06.

[0026] Figure 4 This shows an SEM image of the original product prepared in Example 2.12.

[0027] Figure 5 SEM images of the original products prepared in Examples 2.16, 2.17 and 2.18 are shown.

[0028] Figure 6 The powder XRD patterns of the original products of Examples 2.16, 2.17 and 2.18 are shown.

[0029] Figure 7 Showing the powder XRD patterns of the original and calcined products of Example 3.01.

[0030] Figure 8 This shows an SEM image of the original product prepared in Example 3.01.

[0031] Figure 9 Showing the powder XRD patterns of the original and calcined products of Example 3.02.

[0032] Figure 10 This shows an SEM image of the original product prepared in Example 3.02.

[0033] Figure 11 Showing the powder XRD pattern of the original product of Example 3.04.

[0034] Figure 12 This shows an SEM image of the original product prepared in Example 3.04.

[0035] Figure 13 Showing the projection of EMM-65 along its 12-ring pores.

[0036] Detailed description

[0037] 1-Methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation

[0038] According to a first aspect of the invention, the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I is found to be:

[0039]

[0040] It can be used as a structure directing agent (SDA) in the preparation of zeolites.

[0041] As mentioned above, it is important to identify novel structure-directing agents and more efficient methods for synthesizing molecular sieves, thereby facilitating the preparation of novel molecular sieves and / or reducing the cost of manufacturing known zeolites. The inventors have discovered that the cation of Formula I can be suitably used to prepare novel crystalline materials identified as EMM-64 and EMM-65. These crystalline materials, their synthesis methods, and uses are disclosed herein. The inventors have also discovered that the cation of Formula I can be used to prepare RTH-framework type aluminosilicate molecular sieves. The methods described herein, as well as the RTH-framework type aluminosilicate molecular sieves obtainable by these methods and their uses, are also described herein.

[0042] The 1-methyl-6,7-dihydro-5H-cyclopentadienyl[b]pyridin-1-onium cation can be used in any suitable form in the zeolite synthesis mixture, for example, in its hydroxide and / or halide form, such as chloride, bromide, iodide, or fluoride. When SDA is used in its hydroxide form, it also acts as a hydroxyl ion source, providing hydroxyl ions (OH) to the synthesis mixture. When SDA is used in its halide form, it also acts as a halide ion source, providing halide ions (W) to the synthesis mixture. For example, when SDA is used in its fluoride form, it also acts as a fluoride ion source, providing fluoride ions (F) to the synthesis mixture.

[0043] The 1-methyl-6,7-dihydro-5H-cyclopentyl[b]pyridine-1-onium cation of Formula I can be obtained by any suitable method in the art. For example, the iodide form of SDA can be obtained by reacting iodomethane with 6,7-dihydro-5H-cyclopentyl[b]pyridine, or the bromide form of SDA can be obtained by reacting methyl bromethane with 6,7-dihydro-5H-cyclopentyl[b]pyridine. The hydroxide form of the cation can then be obtained by exchanging the iodide salt with hydroxide, for example using an ion exchange resin.

[0044] EMM-64 Crystalline Material

[0045] As a second aspect of the invention, crystalline materials (e.g., zeolites) referred to as EMM-64, methods for preparing these materials, and their uses are described herein.

[0046] "Prepared as is" (or "prepared as is") EMM-64 materials (i.e., prior to heat treatment or other treatments to remove SDA from the pores) typically contain SDA within their pores, which is one of the components in the synthetic mixture. EMM-64 materials 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 or "calcined" EMM-64 materials.

[0047] In one embodiment, the EMM-64 crystalline material of the present invention, in its calcined form, has an X-ray diffraction pattern comprising at least 9, 10, or 11 peaks, or preferably all, selected from Table 1, denoted by °2θ:

[0048] Table 1

[0049] °2θ(±0.20) Relative intensity [100 x I / (Io)] 8.11 60-100 9.10 10-20 12.86 10-20 13.41 10-30 15.20 30-60 19.74 20-40 19.94 10-30 20.65 40-70 23.78 40-70 27.11 10-20 27.70 10-30 28.70 10-30

[0050] In another embodiment, the EMM-64 crystalline material, in its calcined form, may have an X-ray diffraction pattern of at least 9, 10, or 11 peaks, or preferably all, selected from Table 1A, represented by °2θ and d-interval values, wherein the d-interval values ​​have a deviation determined based on the corresponding deviation ±0.20°2θ when converted to the corresponding d-interval values ​​using Bragg's law:

[0051] Table 1A

[0052]

[0053] XRD patterns with the XRD peaks described herein were obtained using Cu(K) α )radiation.

[0054] In another embodiment, the EMM-64 crystalline material (whether it has SDA or some or all of the SDA has been removed) has a framework defined by the connectivity of tetrahedral (T) atoms in the unit cell as shown in Table 2, wherein the tetrahedral (T) atoms are connected via bridging atoms.

[0055] Table 2

[0056]

[0057] Topologically equivalent atoms have the same "T-type" symbol at their positions.

[0058] b. The size and number of the smallest rings at each angle of the T-atom (M.O'Keeffe and SHyde, Zeolites, 19, 370 (1997)).

[0059] Connectivity can be determined, for example, using the public domain software TOTOPOL, such as MMJTreacy, and is available from http: / / america.iza-structure.org / IZA-SC / check_topology.php (see, for example, MMJTreacy, I. Rivin, E. Balkovsky, K. H.R. Andall and M.D. Foster, Microporous and Mesoporous Materials, 74, 121-132 (2004)). 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, tetrahedral atoms may be selected from B, Al, or Si, or mixtures thereof. For example, tetrahedral atoms may contain either Si or Al. Bridging atoms may be selected from O, N, and C, or mixtures thereof. Bridging atoms may contain either 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) can be introduced from various components used in zeolite preparation, such as silica sources. Bridging atoms (N) can be introduced into zeolites after SDA removal.

[0060] In another embodiment, the EMM-64 material (whether it has SDA or some or all of the SDA has been removed) can be identified as having a structure that: (a) can be represented as a tetragonal crystal space group I 41 2 2, wherein the cell size is and (b) has a 3D 8-ring channel system, which is unique in that the framework is chiral.

[0061] In one or more other embodiments, the EMM-64 crystalline material in its calcined form may have a micropore volume of 0.10 to 0.20 (e.g., 0.13) cc / g.

[0062] In one or more other embodiments, the EMM-64 crystalline material in its calcined form may optionally be represented by the molecular formula of Formula II:

[0063] (m)X2O3:YO2 (Formula II),

[0064] Where 0 ≤ m ≤ 0.025, X is a trivalent element, and Y is a tetravalent element. Y can be selected from Si, Ge, Sn, Ti, and Zr, or mixtures thereof. For example, Y can contain Si. X can be selected from Al, B, Fe, and Ga, or mixtures thereof. For example, X can contain Al and / or B, especially Al. The oxygen atom in Formula II can be replaced by a carbon atom (e.g., in the form of CH2), which can come from the source material used to produce those components that make up pristine EMM-64. The oxygen atom in Formula II can also be replaced by a nitrogen atom, for example, after SDA has been removed. Formula II can represent the skeleton of a typical EMM-64 material in calcined form, but this is not the only representation of EMM-64 material. After appropriate treatment to remove SDA and impurities, EMM-64 material may contain SDA and / or impurities, which are not included in Formula II. In addition, Formula II does not include protons and charge-compensating ions that may be present in calcined EMM-64 material.

[0065] The variable m represents the molar ratio between X₂O₃ and YO₂ in Equation II. For example, when m is 0.025, the molar ratio between YO₂ and X₂O₃ is 40, and the molar ratio between Y and X is 20 (e.g., the molar ratio of Si / Al is 20). m can vary from 0 to 0.025, for example, at least 0 or at least 0.0005 or at least 0.001 to at most 0.025 or at most 0.017, for example, 0.005 to 0.025. The molar ratio between Y and X can be from 20 to infinity, for example, at least 20 or at least 30 and up to infinity or at most 1000 or at most 500, for example, 20 to 100.

[0066] The original state of the EMM-64 crystalline material of the present invention (i.e., before processing to remove SDA from the pores) can have an X-ray diffraction pattern comprising at least 7 or 8 peaks, or preferably all of them, selected from Table 3, denoted by °2θ:

[0067] Table 3

[0068] °2θ(±0.20) Relative intensity [100 x I / (Io)] 8.08 20-40 15.20 10-30 19.54 30-60 19.94 10-30 20.56 50-80 23.79 60-100 27.12 10-30 27.69 20-40 28.50 20-40

[0069] In another embodiment, the EMM-64 crystalline material, in its original state, may have an X-ray diffraction pattern comprising at least 7 or 8 peaks, or preferably all, selected from Table 3A, represented by °2θ and d-interval values, wherein the d-interval values ​​have a deviation determined based on the corresponding deviation ±0.20°2θ when converted to the corresponding d-interval values ​​using Bragg's law:

[0070] Table 3A

[0071]

[0072] XRD patterns with the XRD peaks described herein were obtained using Cu(K) α )radiation.

[0073] In one or more embodiments, the preparation of the original EMM-64 crystalline material can optionally be represented by the molecular formula of Formula III:

[0074] (n)Q:(m)X2O3:YO2 (Formula III),

[0075] Where 0 ≤ n ≤ 0.2, 0 ≤ m ≤ 0.025, Q is the 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I, X is a trivalent element as defined in Formula II, and Y is a tetravalent element as defined in Formula II. Formula III can represent the framework of a typical pre-formed EMM-64 material with a structure-directing agent (Q), but this is not the only representative of such a material. Pre-formed EMM-64 materials may contain impurities, which are not included in Formula III. In addition, Formula III does not include protons and charge-compensating ions that may be present in pre-formed EMM-64 materials.

[0076] The variable m represents the molar ratio between X₂O₃ and YO₂ in Equation III. The value of the variable m in Equation III is the same as that described with respect to Equation II.

[0077] The variable n represents the molar relationship between Q and YO2 in Equation III. For example, when n is 0.1, the molar ratio between Q and YO2 is 0.1. The molar ratio between Q and YO2 can be in the range of 0 to 0.2, for example, 0.02 to 0.1, or 0.03 to 0.06.

[0078] According to a second aspect of the present invention, a method for preparing EMM-64 crystalline material may include the following steps:

[0079] (a) Preparing a synthetic mixture comprising water, a source of an oxide of a tetravalent element (Y), optionally a source of an oxide of a trivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), and optionally a source of an alkali metal and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises a 1-methyl-6,7-dihydro-5H-cyclopentadienyl[b]pyridin-1-onium cation of formula I as defined above, and wherein the synthetic mixture comprises fluoride ions (F) at a molar ratio of at least 0.1 for F / Y;

[0080] (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 crystalline material;

[0081] (c) Recover at least a portion of the crystalline material from step (b); and

[0082] (d) Optionally, the crystalline material recovered in step (c) is treated to remove at least a portion of the structure-directing agent (Q).

[0083] The structure-directing agent (Q) may be present in any suitable form, such as as a halide, such as a chloride or bromide, as a hydroxide, or as a nitrate, for example, in the form of its hydroxide. The structure-directing agent (Q) may be present in the synthetic mixture at a Q / Y molar ratio of 0.01 to 1.0, for example 0.05 to 1.0, or 0.1 to 0.8, or 0.2 to 0.7, or 0.3 to 0.6, for example greater than 0.3, such as 0.5.

[0084] The synthetic mixture contains a source of at least one oxide of a tetravalent element Y, such as Si, Ge, Sn, Ti, and / or Zr, preferably containing Si, more preferably Si. The source of the tetravalent element Y suitable for preparing this synthetic mixture depends on the element Y selected. In embodiments where Y is silicon, suitable Si sources (e.g., silicon oxide sources) include silicates, such as tetraalkyl orthosilicates, such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), pyrolytic silicon dioxide, such as… (Available from Evonik) (Available from Cabot) and (Available from DMS), precipitated silica, for example and 340 (available from Evonik), aqueous colloidal suspensions of alkali metal silicates, such as potassium silicate and sodium silicate, and silica, for example, by EIdu Pont de Nemours under the trade name Sold or sold by Evonik under the trade name Those for sale; preferably silicates, pyrolytic silica, precipitated silica, alkali metal silicates, and colloidal silica. In embodiments where Y is germanium, suitable Ge sources include germanium oxide. In embodiments where Y is titanium, suitable Ti sources include titanium dioxide and titanium tetraalkoxy, such as titanium tetraethoxy (IV) and titanium tetrachloride (IV). In embodiments where Y is tin, suitable Sn sources include tin chloride and tin alkoxy, such as tin ethoxy and tin isopropoxy. In embodiments where Y is zirconium, suitable Zr sources include zirconium chloride and zirconium alkoxy, such as zirconium ethoxy and zirconium isopropoxy.

[0085] The synthetic mixture optionally contains a source of at least one oxide of a trivalent element X, such as Al, B, Fe, and / or Ga; preferably X contains Al and / or B, for example, Al; more preferably X is Al and / or B, for example, Al. The source of the trivalent element X suitable for preparing the synthetic mixture depends on the element X selected. In embodiments where X is aluminum, suitable Al sources (e.g., alumina sources) for this method include aluminum salts, especially water-soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, alkali metal aluminates such as sodium aluminate, and aluminum alkoxylates such as aluminum isopropyloxide, and 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 alkoxylates such as aluminum isopropyloxide, or aluminum metal, such as aluminum in flake form. In embodiments where X is boron, suitable B sources include boric acid and borates such as sodium tetraborate or borax and potassium tetraborate. Boron sources tend to be more soluble than aluminum sources in hydroxide-modified synthesis systems. In embodiments where X is gallium, suitable Ga 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 ferric chloride, ferric nitrate, and ferric oxide.

[0086] In addition to or besides the sources of Y and X (e.g., Si and Al) mentioned above, sources containing both Y and X elements, such as Si and Al sources, can be used. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gel or dried 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, or other macroporous to mesoporous zeolites.

[0087] The synthetic mixture can have a Y / X molar ratio of at least 10 to infinity, particularly at least 20 to infinity, such as 20, 30, or 100 to 500, 1000, or infinity (i.e., containing no X or substantially no X). In a particularly preferred embodiment of this aspect of the invention, Y is Si, optionally X is Al, and the EMM-64 material is a silicate or aluminosilicate.

[0088] The synthetic mixture also contains at least one source of fluoride ions (F). The source of fluoride ions (F) can be any compound capable of releasing fluoride ions in the molecular sieve synthetic mixture. Non-limiting examples of sources of fluoride ions (F) include hydrogen fluoride (HF); salts containing one or more fluoride ions, such as metal fluorides, preferably wherein the metal is sodium, potassium, calcium, magnesium, strontium, or barium; ammonium fluoride (NH4F); and ammonium difluoride (NH4HF2). Particularly convenient sources of fluoride ions are HF, NH4F, and NH4HF2, especially HF. Fluoride ions (F) may be present at an F / Y molar ratio of 0.1 to 1.0, for example, 0.2 to 0.8, or 0.3 to 0.7, for example, 0.3, 0.4, or 0.5.

[0089] The synthetic mixture may optionally also contain at least one source of halide ions (W) different from fluoride ions, which may be selected from chlorides, bromides, or iodides. The source of halide ions (W) can be any compound capable of releasing halide ions in the molecular sieve synthetic mixture. Non-limiting examples of halide ion sources include 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 halides; or tetraalkyl ammonium halides, such as tetramethylammonium halide or tetraethylammonium halide. The halide ions (W) may be present at a W / Y molar ratio of 0 to 0.2, for example, 0 to 0.1, for example, less than 0.1 or even 0.

[0090] Optionally, the synthetic mixture may also contain at least one source of hydroxide ions (OH). For example, hydroxide ions may be present as counterions to the structure-directing agent (Q), 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; for example, from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more generally from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most commonly from sodium hydroxide and / or potassium hydroxide. The synthetic mixture may contain a hydroxide ion source at an OH / Y molar ratio of 0 to 1.5, for example 0 or 0.05 to 1.0 or 0.8, for example 0.1 to 0.8, or 0.2 to 0.7, for example 0.5. Alternatively, the synthetic mixture may not contain a hydroxide ion source.

[0091] Optionally, the synthetic mixture may contain a source of one or more alkali metal or alkaline earth metal cations (M). If present, M is preferably selected from sodium, potassium, lithium, rubidium, calcium, magnesium, and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. The sodium source, when present, may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or a sodium salt, such as NaCl, NaBr, or sodium nitrate. The potassium source, when present, may be potassium hydroxide, potassium aluminate, potassium silicate, or a potassium salt, such as KCl or KBr or potassium nitrate. The lithium source, when present, may be lithium hydroxide or a lithium salt, such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. The rubidium source, when present, may be rubidium hydroxide or a rubidium salt, 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 trivalent element sources X, such as sodium aluminate, sodium tetraborate, potassium tetraborate, sodium gallate, potassium gallate, and / or in one or more tetravalent element sources Y, such as potassium silicate and / or sodium silicate. The synthetic mixture may contain a source of the alkali metal or alkaline earth metal cation (M) at an M / Y molar ratio of 0 to 1.5, for example, 0 or 0.05 to 1.0 or 0.8, such as 0.1, 0.2, or 0.3. Alternatively, the synthetic mixture may not contain the alkali metal or alkaline earth metal cation (M).

[0092] Synthesis can be carried out with or without additional nucleating seeds. If nucleating seeds are added to the synthesis mixture, these seeds may have the same or different structures as EMM-64, such as those derived from previously synthesized EMM-64, and may suitably be present in amounts from about 0.01 ppm to about 10,000 ppm by weight based on the synthesis mixture, for example, from about 100 ppm to about 5,000 ppm by weight based on the synthesis mixture.

[0093] The synthetic mixture typically contains water at an H2O / Y molar ratio of 1 to 100, for example, 1 to 75 or 1 to 50, such as 1, 2, 3, or 4 to 50. Depending on the nature of the components in the base mixture, the amount of solvent in the base mixture (e.g., water from a hydroxide solution, and optionally methanol and ethanol obtained from the hydrolysis of a silica source) can be removed to achieve the desired solvent to Y molar ratio in the synthetic mixture. Suitable methods for reducing the solvent content may include evaporation in a static or flowing atmosphere, such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. When excessive water is removed in the solvent removal process, water can be added to the resulting mixture to achieve the desired H2O / Y molar ratio. In some instances, water removal is not necessary when the preparation has a sufficient H2O / Y molar ratio.

[0094] Carbon in the form of CH2 can be present in various sources of those components used to prepare EMM-64, such as tetravalent element sources (silicon dioxide sources) or trivalent element sources (alumina sources), and can be introduced into the EMM-64 framework as bridging atoms. After SDA has been removed, nitrogen atoms can be introduced into the framework of the EMM-64 material as bridging atoms.

[0095] In one or more aspects, the synthetic mixture after solvent adjustment (e.g., where the desired water to silica ratio is achieved) can be mixed mechanically, such as by stirring or high-shear blending, to ensure proper homogenization of the base mixture, for example using dual asymmetric centrifugal mixing (e.g., FlackTek Speedmixer) at a mixing speed of 1000 to 3000 rpm (e.g., 2000 rpm).

[0096] The synthetic mixture is then subjected to crystallization conditions suitable for the formation of EMM-64 material. Crystallization of EMM-64 material can be carried out under static or stirred conditions in a suitable reactor vessel, such as a convection furnace maintained at a suitable temperature. Lined or stainless steel autoclave.

[0097] The crystallization in step (b) of this method is typically carried out at a temperature of 100°C to 200°C, for example, 150°C to 170°C, for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be reduced. 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 (e.g., 1 to 12, 14, or 16 days, or 1 to 7 days). The crystallization time can be determined by methods known in the art, for example, by sampling the synthetic mixture at different times and determining the yield of the precipitated solids and the X-ray crystallinity. Unless otherwise stated, the measured temperature is the temperature of the environment surrounding the material being heated, such as the temperature of the atmosphere in which the material is heated.

[0098] Typically, EMM-64 products are formed as solutions and can be recovered using standard methods such as centrifugation or filtration. Separated EMM-64 products can also be washed, recovered by centrifugation or filtration, and dried.

[0099] The molecular sieve of the present invention, when used as an adsorbent or as a catalyst in an organic compound conversion process, can be at least partially dehydrated (e.g., dried). This can be carried out by heating to a temperature in the range of 80°C to 500°C, for example, 90°C to 370°C, in an atmosphere such as air, nitrogen, etc., and at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure for 30 minutes to 48 hours. 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 achieve sufficient dehydration.

[0100] 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 virgin EMM-64 material recovered from step (c) can be subjected to heat treatment or other treatments to remove some or all of the SDA introduced into the pores during synthesis. Heat treatment (e.g., calcination) of the virgin EMM-64 material typically involves exposing the material in a furnace to a high temperature sufficient to remove some or all of the SDA in an atmosphere selected from air, nitrogen, ozone, or mixtures thereof. Although pressures below atmospheric pressure can be used for heat treatment, atmospheric pressure is preferred for convenience. 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 ambient temperature surrounding the sample. Heat treatment (e.g., calcination) can be carried out in a box furnace in dry air, which has been exposed to a drying tube containing a desiccant for removing moisture from the air. This heating typically involves calcination for at least 1 minute to a period not exceeding 1 day or at most several days. The heating can be carried out first in a nitrogen atmosphere, and then the atmosphere can be switched to air and / or ozone.

[0101] EMM-64 material can also undergo ion exchange treatment, for example using aqueous solutions of 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 obtaining a molecular sieve in acid form. The initial cations used to prepare the virgin material, such as alkali metal cations, can be replaced by other cations through ion exchange, to the desired extent. Preferred cations for replacement may include hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. The ion exchange step can be performed after drying to prepare the virgin molecular sieve. The ion exchange step can be performed before or after the calcination step.

[0102] Molecular sieves can also undergo other treatments, such as steam treatment and / or solvent washing. These treatments are well known to those skilled in the art and are used to improve the desired properties of the molecular sieves.

[0103] EMM-65 Crystalline Material

[0104] As a third aspect of the invention, crystalline materials (e.g., zeolites) referred to as EMM-65, methods for preparing these materials, and their uses are described herein.

[0105] "Prepared as is" (or "prepared as is") EMM-65 materials (i.e., prior to heat treatment or other treatments to remove SDA from the pores) typically contain SDA within their pores, which is one of the components in the synthetic mixture. EMM-65 materials 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 or "calcined" EMM-65 materials.

[0106] In one embodiment, the EMM-65 crystalline material of the present invention, in its calcined form, has an X-ray diffraction pattern comprising at least 8, 9, or 10 peaks, or preferably all, selected from Table 4, denoted by °2θ:

[0107] Table 4

[0108] °2θ(±0.20) Relative intensity [100 x I / (Io)] 6.58 60-100 7.91 50-80 8.56 30-60 10.30 20-40 19.76 20-40 20.52 10-30 21.83 10-30 24.07 20-40 24.76 10-20 25.55 10-20 26.54 10-20

[0109] In another embodiment, the EMM-65 crystalline material, in its calcined form, may have an X-ray diffraction pattern comprising at least 8, 9, or 10 peaks, or preferably all, selected from Table 4A, represented by °2θ and d-interval values, wherein the d-interval values ​​have a deviation determined based on the corresponding deviation ±0.20°2θ when converted to the corresponding d-interval values ​​using Bragg's law:

[0110] Table 4A

[0111]

[0112] XRD patterns with the XRD peaks described herein were obtained using Cu(K) α )radiation.

[0113] In another embodiment, the EMM-65 crystalline material (whether it has SDA or some or all of the SDA has been removed) has a framework defined by the connectivity of tetrahedral (T) atoms in the unit cell as shown in Table 5, wherein the tetrahedral (T) atoms are connected via bridging atoms.

[0114] Table 5

[0115]

[0116] Topologically equivalent atoms have the same "T-type" symbol at their positions.

[0117] b The size and number of the smallest rings at each angle of the T-atom (M.O'Keeffe and SHyde, Zeolite, 19, 370 (1997)).

[0118] Connectivity can be determined, for example, using the public domain software TOTOPOL, such as MMJTreacy, and is available from http: / / america.iza-structure.org / IZA-SC / check_topology.php (see, for example, MMJTreacy, I. Rivin, E. Balkovsky, K. H.R. Andall and M.D. Foster, Microporous and Mesoporous Materials, 74, 121-132 (2004)). 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, tetrahedral atoms may be selected from B, Al, or Si, or mixtures thereof. For example, tetrahedral atoms may contain either Si or Al. Bridging atoms may be selected from O, N, and C, or mixtures thereof. Bridging atoms may contain either 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) can be introduced from various components used in zeolite preparation, such as silica sources. Bridging atoms (N) can be introduced into zeolites after SDA removal.

[0119] In another embodiment, the EMM-65 material (whether it has SDA or some or all of the SDA has been removed) can be identified as having a structure in which: (a) it can be represented by the orthogonal space group Pmmn2, wherein the cell size is and (b) has a 1D 12-ring channel system, which has The pore size.

[0120] In one or more other embodiments, the EMM-65 crystalline material in its calcined form may have a micropore volume of 0.10 to 0.20 (e.g., 0.13) cc / g.

[0121] In one or more other embodiments, the EMM-65 crystalline material in its calcined form may optionally be represented by the molecular formula of Formula IV:

[0122] (m)B2O3:SiO2 (Formula IV),

[0123] Where 0.005 ≤ m ≤ 0.05. The oxygen atom in Formula IV can be replaced by a carbon atom (e.g., in the form of CH2), which can originate from the source material used to produce those components that make up pristine EMM-65. The oxygen atom in Formula IV can also be replaced by a nitrogen atom, for example, after SDA has been removed. Formula IV can represent the skeleton of a typical EMM-65 material in calcined form, and this is not to imply the only representative of EMM-65 materials. EMM-65 materials may contain SDA and / or impurities after appropriate treatment to remove SDA and impurities, which are not included in Formula IV. Furthermore, Formula IV does not include protons and charge-compensating ions that may be present in calcined EMM-65 materials.

[0124] In this embodiment, the EMM-65 crystalline material is in the form of borosilicate, and the variable m represents the molar ratio between B2O3 and SiO2 in formula IV. For example, when m is 0.025, the molar ratio between SiO2 and B2O3 is 40, and the molar ratio between Si and B is 20. m can vary from 0.005 to 0.05, for example, at least 0.01 to 0.033, such as 0.025. The molar ratio between Si and B can be from 10 to 100, for example, from 15 to 50, such as 20.

[0125] The original state of the EMM-65 crystalline material of the present invention (i.e., before processing to remove SDA from the pores) can have an X-ray diffraction pattern comprising at least 18, 19, or 20 peaks, or preferably all of them, selected from Table 6, denoted by °2θ:

[0126] Table 6

[0127] °2θ(±0.20) Relative intensity [100 x I / (Io)] 6.64 30-60 7.97 40-70 8.63 30-60 10.35 10-30 15.44 10-30 16.24 10-20 18.76 20-40 19.85 20-40 20.61 30-60 21.93 30-60 23.72 20-40 24.18 60-100 24.84 10-30 25.64 30-60 26.56 20-40 27.60 10-20 28.23 20-40 30.84 10-20 33.47 10-20 36.04 20-40 37.25 10-30

[0128] In another embodiment, the EMM-65 crystalline material, in its original form, may have an X-ray diffraction pattern comprising at least 18, 19, or 20 peaks, or preferably all, selected from Table 6A, represented by °2θ and d-interval values, wherein the d-interval values ​​have a deviation determined based on a corresponding deviation ±0.20°2θ when converted to the corresponding d-interval values ​​using Bragg's law:

[0129] Table 6A

[0130]

[0131] XRD patterns with the XRD peaks described herein were obtained using Cu(K) α )radiation.

[0132] In one or more embodiments, the preparation of the original EMM-65 crystalline material can optionally be represented by the molecular formula of formula V:

[0133] (n)Q:(m)B2O3:SiO2 (Formula V),

[0134] where 0 ≤ n ≤ 0.2, 0.005 < m ≤ 0.05, and Q is the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridin-1-ium cation of Formula I. Formula V may represent the framework of the as-made EMM-65 material with the structure-directing agent (Q), but this does not mean the only representation of such material. The as-made EMM-65 material may contain impurities, which are not included in Formula V. Additionally, Formula V does not include the protons and charge-compensating ions that may be present in the as-made EMM-65 material.

[0135] The variable m represents the molar ratio relationship between B2O3 and SiO2 in Formula V. The value of the variable m in Formula V is the same as those described above for Formula IV.

[0136] The variable n represents the molar ratio relationship between Q and SiO2 in Formula V. For example, when n is 0.1, the molar ratio between Q and SiO2 is 0.1. The molar ratio between Q and SiO2 can range from 0 to 0.2, such as 0.02 to 0.1, such as 0.03 to 0.06.

[0137] According to the third aspect of the present invention, a method for preparing an EMM-65 crystalline material may comprise the following steps:

[0138] (a) Preparing a synthesis mixture that contains water, a source of silica, a source of boron (B), a structure-directing agent (Q), optionally a source of hydroxide ions (OH), and optionally a source of alkali metal and / or alkaline earth metal elements (M), where the structure-directing agent (Q) contains the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridin-1-ium cation of Formula I as defined above, and where the synthesis mixture contains fluoride ions (F) at an F / Si molar ratio of less than 0.1;

[0139] (b) Heating the synthesis mixture under crystallization conditions including a temperature of 100 °C to 200 °C for a time sufficient to form crystals of the crystalline material;

[0140] (c) Recovering at least a portion of the crystalline material from step (b); and

[0141] (d) Optionally, treating the crystalline material recovered in step (c) to remove at least a portion of the structure-directing agent (Q).

[0142] The structure-directing agent (Q) may be present in any suitable form, such as as a halide, such as a chloride or bromide, as a hydroxide, or as a nitrate, for example, in the form of its hydroxide. The structure-directing agent (Q) may be present in the synthetic mixture at a Q / Si molar ratio of 0.01 to 1.0, for example 0.05 to 1.0, or 0.1 to 0.8, or 0.1 to 0.5, for example 0.1 to less than 0.5, for example 0.2 or 0.3.

[0143] The synthetic mixture contains at least one silica source (e.g., silicon dioxide). Suitable silica sources for this method include silicate esters, such as tetraalkyl orthosilicates, such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), pyrolytic silica, such as... (Available from Evonik) (Available from Cabot) and (Available from DMS), precipitated silica, for example and 340 (available from Evonik), aqueous colloidal suspensions of alkali metal silicates, such as potassium silicate and sodium silicate, and silica, for example, by EIdu Pont de Nemours under the trade name Sold or sold by Evonik under the trade name Those for sale; preferably silicates, pyrolytic silica, precipitated silica, alkali metal silicates and colloidal silica.

[0144] The synthetic mixture contains at least one boron (B) source. Suitable boron sources include boric acids and borates, such as sodium tetraborate or borax and potassium tetraborate.

[0145] The synthetic mixture may have a Si / B molar ratio in the range of at least 10 to 100, for example at least 10 or at least 15 or at least 20 to at most 100 or at most 75 or at most 50, for example 20.

[0146] The synthetic mixture used to prepare EMM-65 materials contains fluoride ions (F) in an F / Si molar ratio of less than 0.1, for example, 0 to less than 0.1, or 0 to 0.05, or 0 to 0.01, for example, 0. In particular, the synthetic mixture used to prepare EMM-65 materials is substantially free of fluoride ions (F). This means that no significant source of fluoride ions is added to the synthetic mixture, for example, the synthetic mixture has an F / Si molar ratio of less than 0.1, especially less than 0.05, for example, less than 0.01 or even less than 0.005, for example, 0. When present, the fluoride ions (F) can be derived from any compound capable of releasing fluoride ions in the molecular sieve synthetic mixture, such as hydrogen fluoride (HF); salts containing one or more fluoride ions, such as metal fluorides, preferably wherein the metal is sodium, potassium, calcium, magnesium, strontium, or barium; ammonium fluoride (NH4F); and ammonium difluoride (NH4HF2). Small amounts of fluoride ions (F) may also be present as impurities, for example, in the presence of an optional alkali metal or alkaline earth metal cation (M).

[0147] The synthetic mixture may optionally contain at least one source of halide ions (W) different from fluoride ions, which may be selected from chlorides, bromides, or iodides. The source of halide ions (W) can be any compound capable of releasing halide ions in the molecular sieve synthetic mixture. Non-limiting examples of halide ion sources include 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 halides; or tetraalkyl ammonium halides, such as tetramethylammonium halide or tetraethylammonium halide. The halide ions (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. In a preferred embodiment, the synthetic mixture may be substantially free of halide ions (W).

[0148] Optionally, the synthetic mixture may also contain at least one source of hydroxide ions (OH). Suitable hydroxide ion sources may also be selected from 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 generally from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most commonly from sodium hydroxide and / or potassium hydroxide. The synthetic mixture may contain a hydroxide ion source at an OH / Si molar ratio of 0 to 1.5, for example 0 or 0.05 to 1.0 or 0.8, for example 0.1 to 0.8 or 0.2 to 0.7, for example 0.3, 0.4, or 0.5. Alternatively, the synthetic mixture may not contain a hydroxide ion source.

[0149] Optionally, the synthetic mixture may contain a source of one or more alkali metal or alkaline earth metal cations (M). If present, M is preferably selected from sodium, potassium, lithium, rubidium, calcium, magnesium, and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. The sodium source, when present, may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or a sodium salt, such as NaCl, NaBr, or sodium nitrate. The potassium source, when present, may be potassium hydroxide, potassium aluminate, potassium silicate, or a potassium salt, such as KCl or KBr or potassium nitrate. The lithium source, when present, may be lithium hydroxide or a lithium salt, such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. The rubidium source, when present, may be rubidium hydroxide or a rubidium salt, 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 trivalent element X sources, such as sodium aluminate, sodium tetraborate, potassium tetraborate, sodium gallate, potassium gallate, and / or in one or more tetravalent element Y sources, such as potassium silicate and / or 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, for example, 0 or 0.05 to 1.0 or 0.8, for example, less than 0.15, for example, 0.1. Alternatively, the synthetic mixture may not contain the alkali metal or alkaline earth metal cation (M).

[0150] Synthesis can be carried out with or without additional nucleating seeds. If nucleating seeds are added to the synthesis mixture, these seeds may have the same or different structures as EMM-65, such as those derived from previously synthesized EMM-65, and may suitably be present in amounts from about 0.01 ppm to about 10,000 ppm by weight based on the synthesis mixture, for example, from about 100 ppm to about 5,000 ppm by weight based on the synthesis mixture.

[0151] The synthetic mixture typically contains water at an H₂O / Si molar ratio of 1 to 100, or 1 to 75, for example, 1 to 50, for example, at least 5, 10, or 20 to at most 50, for example, 20-40. Depending on the nature of the components in the base mixture, the amount of solvent in the base mixture (e.g., water from a hydroxide solution, and optionally methanol and ethanol obtained from the hydrolysis of a silica source) can be removed to achieve the desired solvent-to-Y molar ratio in the synthetic mixture. Suitable methods for reducing the solvent content may include evaporation in a static or flowing atmosphere, such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. When excessive water is removed in the solvent removal process, 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.

[0152] Carbon in the form of CH2 can be present in various sources of those components used to prepare EMM-65, such as tetravalent element sources (silicon dioxide sources) or trivalent element sources (alumina sources), and can be introduced into the EMM-65 framework as bridging atoms. After SDA has been removed, nitrogen atoms can be introduced into the framework of the EMM-65 material as bridging atoms.

[0153] In one or more aspects, the synthetic mixture after solvent adjustment (e.g., where the desired water to silica ratio is achieved) can be mixed mechanically, such as by stirring or high-shear blending, to ensure proper homogenization of the base mixture, for example using dual asymmetric centrifugal mixing (e.g., FlackTek Speedmixer) at a mixing speed of 1000 to 3000 rpm (e.g., 2000 rpm).

[0154] The synthetic mixture is then subjected to crystallization conditions suitable for the formation of EMM-65 material. Crystallization of EMM-65 material can be carried out under static or stirred conditions in a suitable reactor vessel, such as a polypropylene tank, or in a convection furnace maintained at a suitable temperature. Lined or stainless steel autoclave.

[0155] The crystallization in step (b) of this method is typically carried out at a temperature of 100°C to 200°C, for example, 150°C to 170°C, for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be reduced. 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 (e.g., 1 to 12, 14, or 16 days, or 1 to 7 days). The crystallization time can be determined by methods known in the art, for example, by sampling the synthetic mixture at different times and determining the yield of the precipitated solids and the X-ray crystallinity. Unless otherwise stated, the measured temperature is the temperature of the environment surrounding the material being heated, such as the temperature of the atmosphere in which the material is heated.

[0156] Typically, EMM-65 products are formed in solution and can be recovered using standard methods such as centrifugation or filtration. Separated EMM-65 products can also be washed, recovered by centrifugation or filtration, and dried.

[0157] The molecular sieve of the present invention, when used as an adsorbent or as a catalyst in an organic compound conversion process, can be at least partially dehydrated (e.g., dried). This can be carried out by heating to a temperature in the range of 80°C to 500°C, for example, 90°C to 370°C, in an atmosphere such as air, nitrogen, etc., and at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure for 30 minutes to 48 hours. 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 achieve sufficient dehydration.

[0158] 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 virgin EMM-65 material recovered from step (c) can be subjected to heat treatment or other treatments to remove some or all of the SDA introduced into the pores during synthesis. Heat treatment (e.g., calcination) of the virgin EMM-65 material typically involves exposing the material in a furnace to a high temperature sufficient to remove some or all of the SDA in an atmosphere selected from air, nitrogen, ozone, or mixtures thereof. Although pressures below atmospheric pressure can be used for heat treatment, atmospheric pressure is preferred for convenience. 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 ambient temperature surrounding the sample. Heat treatment (e.g., calcination) can be carried out in a box furnace in dry air, which has been exposed to a drying tube containing a desiccant for removing moisture from the air. Heating typically lasts from at least 1 minute to at most 1 day or several days. The heating can be carried out first in a nitrogen atmosphere, and then the atmosphere can be switched to air and / or ozone.

[0159] EMM-65 material can also undergo ion exchange treatment, for example using aqueous solutions of 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 obtaining a molecular sieve in acid form. The initial cations used to prepare the virgin material, such as alkali metal cations, can be replaced by other cations through ion exchange, to the desired extent. Preferred cations for replacement may include hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. The ion exchange step can be performed after drying to prepare the virgin molecular sieve. The ion exchange step can be performed before or after the calcination step.

[0160] Optionally, aluminum atoms can be introduced into the EMM-65 material framework (where some or all of the SDA has been removed) in an exchange process following the hydrothermal synthesis reaction. Boron-containing framework silicates (e.g., borosilicates) can be particularly effective for the exchange with aluminum atoms. This exchange process may include exposing the EMM-65 material to an aluminum source, such as an aqueous solution of an aluminum salt, under conditions sufficient to exchange at least a portion and at most substantially all of the boron atoms in the framework silicate with aluminum atoms. For example, calcined borosilicate EMM-65 material can be converted into aluminosilicates by heating the boron-containing calcined EMM-65 material together with a solution of aluminum sulfate, aluminum nitrate, aluminum chloride, and / or aluminum acetate (e.g., in a sealed autoclave in a convection furnace at 100°C or at the boiling point temperature in an open system). The aluminum-treated EMM-65 material can then be recovered by filtration and washing with deionized water. The resulting aluminum-exchanged crystalline EMM-65 material can optionally be represented by the molecular formula of Formula VI:

[0161] (m)Al2O3:SiO2 (Formula VI),

[0162] Where 0.005 ≤ m ≤ 0.05. The variable m represents the molar ratio between Al₂O₃ and SiO₂ in Formula VI. The values ​​of the variable m in Formula VI are the same as those described above regarding Formula IV. The oxygen atom in Formula VI may be replaced by a carbon atom (e.g., in the form of CH₂) and / or a nitrogen atom. After appropriate treatment to remove SDA and impurities, the material may contain SDA and / or impurities, which are not included in Formula VI; and Formula VI does not include any protons and charge-compensating ions that may be present. Formula VI can represent the framework of a typical aluminum-exchanged EMM-65 material in calcined form, but this is not the only representative of aluminum-exchanged EMM-65 materials.

[0163] Molecular sieves can also undergo other treatments, such as steam treatment and / or solvent washing. These treatments are well known to those skilled in the art and are used to improve the desired properties of the molecular sieves.

[0164] Applications of EMM-64 and EMM-65 materials

[0165] The EMM-64 and EMM-65 materials according to the second and third aspects of the present invention (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 conversion processes, such as the conversion of organic compounds to conversion products.

[0166] EMM-64 and EMM-65 materials (with some or all of SDA removed) can be used as adsorbents, for example, to separate at least one component from a mixture of multiple components with different adsorption characteristics for the material in the gas or liquid phase. Thus, at least one component can be partially or substantially completely separated from a mixture of multiple components with different adsorption characteristics for the EMM-64 or EMM-65 material by contacting the mixture with the EMM-64 or EMM-65 material to selectively adsorb one component. 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 can be contacted with an adsorbent comprising the EMM-64 or EMM-65 material of the present invention under effective adsorption conditions, thereby forming an adsorption product and an effluent product. One or more desired components can be recovered from the adsorption product or the effluent product.

[0167] EMM-64 and EMM-65 materials (with some or all of SDA removed) can also be used as catalysts to catalyze a wide variety of organic conversion processes. Examples of chemical conversion processes effectively catalyzed by the EMM-64 and EMM-65 materials described herein (alone or in combination with one or more other catalytically active materials, including combinations with other crystalline catalysts) include those processes requiring catalysts with acid activity. Examples of organic conversion processes catalyzed by the EMM-64 or EMM-65 materials described herein include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, alkyl transfer reactions, dealkylation, hydrodecyclization, disproportionation, oligomerization, dehydrocyclization, and combinations thereof. The conversion of hydrocarbon feedstocks can be carried out in any convenient mode, such as in a fluidized bed, moving bed, or fixed bed reactor, depending on the desired process type.

[0168] EMM-64 and EMM-65 materials can be formulated into product compositions by combining them with other materials, such as binders and / or matrix materials, which provide additional stiffness to the final product. These other materials can be inert or catalytically active.

[0169] For example, EMM-64 and EMM-65 materials can be combined with another material that can withstand the temperatures and other conditions used during use. Such materials include synthetic or natural zeolites, and inorganic materials such as clay, silica, and / or metal oxides such as alumina, or mixtures thereof. The metal oxides can 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 a resistant material in conjunction with EMM-64 or EMM-65, i.e., in combination with the material or during synthesis to produce as-is EMM-64 or EMM-65 crystals (which are active), tends to alter the conversion rate and / or catalyst selectivity in certain organic conversion processes. Inactive resistant materials suitably act as diluents to control the conversion amount in a given process, thereby obtaining the product in an economical and orderly manner without using other means of controlling the reaction rate. These materials can be incorporated into natural 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 are beneficial because it is desirable to prevent catalysts from breaking into powdery materials in commercial applications.

[0170] Available natural clays include the montmorillonite and kaolinite families, which include subbentonites, and kaolinite commonly known as Dixie, McNamee, Georgia, and Florida clays, or other clays whose main mineral components are halloysite, kaolinite, dickite, nacrite, or anauxite. These clays can be used in their original, unprocessed state, or after calcination, acid treatment, or chemical modification. Binders that can be used in conjunction with EMM-64 and EMM-65 materials 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.

[0171] In addition to the materials mentioned above, EMM-64 and EMM-65 materials 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.

[0172] These binder materials are resistant to temperature and other conditions, such as mechanical grinding, which occurs in various hydrocarbon separation processes. Therefore, EMM-64 and EMM-65 materials can be used in extrusion form with the binder. They are typically bonded by forming pellets, spheres, or extrusions. Extrusions are typically formed by extruding molecular sieves optionally in the presence of the binder, followed by drying and calcining the resulting extrusion. Further processing, such as steam treatment and / or ion exchange, can be performed as needed. Molecular sieves can optionally be combined with materials having a minimum thickness of 100 μm. 2 / g of surface area adhesive bond, for example at least 200m 2 / g, optionally at least 300m 2 / g.

[0173] The relative ratio of molecular sieves and inorganic oxide matrix can vary over a wide range, with the molecular sieve content ranging from about 1 to 100% by weight, especially when the composite is prepared in extrusion form, the content is more typically about 2 to 95% by weight of the composite, optionally about 20 to 90% by weight.

[0174] EMM-64 and EMM-65 materials can also be closely integrated with hydrogenated components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals like platinum or palladium, where a hydrogenation-dehydrogenation function is to be performed. These hydrogenated components can be incorporated into the composition by one or more of the following methods: co-crystallization; exchange into the composition to include a Group IIIA element, such as aluminum, in the structure; or close physical mixing. These components can also be impregnated into or onto the EMM-64 or EMM-65 material, for example, by treating the molecular sieve with ions containing hydride metals. For example, in the case of platinum, suitable platinum compounds include chloroplatinic acid, platinum(II) chloride, and various compounds containing platinumamine complexes. Combinations of metals and introduction methods can also be used.

[0175] Those skilled in the art will understand that the EMM-64 and EMM-65 of the present invention 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 molecular sieves of different framework types that coexist with EMM-64 materials are, for example, AST and / or ITQ framework type molecular sieves. Typical crystalline materials that coexist with EMM-65 materials are, for example, quartz, cubic quartz, and / or layered phase materials such as kenyaite. The EMM-64 and EMM-65 materials of the present invention are preferably substantially free of impurities. As used herein, the term "substantially free of impurities" (or, in other words, "substantially pure") means that EMM-64 and EMM-65 materials contain 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 these impurities (or "non-EMM-64 and non-EMM-65 materials"), wherein the weight percentage (wt%) value is based on the total weight of the impurities and pure EMM-64 or pure EMM-65. The amount of impurities can be suitably determined by powder XRD, rotating electron diffraction, and / or SEM / TEM (e.g., different crystal morphologies).

[0176] The EMM-64 and EMM-65 materials of the present invention 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 represent a regular and / or ordered molecular arrangement with an identifiable crystal lattice. For example, crystalline EMM-64 or EMM-65 may 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 a majority of the weight (greater than 50% by weight) of a sample of the material is crystalline, and the remainder of the sample is amorphous. In one or more aspects, the substantially crystalline sample has at least 95% crystallinity (e.g., 5% amorphous form), at least 96% crystallinity (e.g., 4% amorphous form), at least 97% crystallinity (e.g., 3% amorphous form), at least 98% crystallinity (e.g., about 2% amorphous form), at least 99% crystallinity (e.g., 1% amorphous form), and 100% crystallinity (e.g., 0% amorphous form).

[0177] RTH framework type aluminosilicate molecular sieves

[0178] As a fourth aspect of the invention, a method for preparing RTH framework-type aluminosilicate molecular sieves (e.g., RTH zeolites), RTH framework-type aluminosilicate molecular sieves obtainable by said method, and their uses are described herein.

[0179] In one embodiment, the method for preparing RTH framework-type aluminosilicate molecular sieves includes the following steps:

[0180] (a) Prepare a synthetic mixture comprising water, a source of silica, a source of alumina, a structure directing agent (Q), optionally a source of hydroxyl ions (OH), and optionally a source of an alkali metal and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises a 1-methyl-6,7-dihydro-5H-cyclopentadienyl[b]pyridin-1-onium cation of formula I as defined above, and wherein the synthetic mixture comprises fluoride ions (F) in an F / Si molar ratio of less than 0.1;

[0181] (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 molecular sieve;

[0182] (c) Recover at least a portion of the molecular sieve crystals from step (b); and

[0183] (d) Optionally, the molecular sieve crystals recovered in step (c) are treated to remove at least a portion of the structure directing agent (Q).

[0184] Known methods for preparing RTH framework-type aluminosilicate molecular sieves use N-ethyl-N-methyl-5,7,7-trimethyl-azaonium bicyclo[4.1.1]octane cations or 2,6-methyl-N-methylpyridinium cations as SDAs. Surprisingly, the method described in the fourth aspect of the present invention is capable of preparing aluminosilicate RTH zeolites with particularly low Si / Al molar ratios. The method of the fourth aspect is also advantageous because it enables the preparation of aluminosilicate RTH zeolites using inexpensive SDAs, especially SDAs that are easier to prepare and cheaper than N-ethyl-N-methyl-5,7,7-trimethyl-azaonium bicyclo[4.1.1]octane cations.

[0185] In a fourth aspect of the invention, 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, in the form of its hydroxide. The structure-directing agent (Q) may be present in the synthetic mixture at a Q / Si molar ratio of 0.01 to 1.0, for example 0.05 to 1.0, or 0.1 to 0.8, or 0.1 to 0.5, for example 0.1 to less than 0.5, for example 0.2 or 0.3.

[0186] The synthetic mixture contains at least one source of silica (e.g., silicon dioxide). Suitable silica sources for this method include silicates, such as tetraalkyl orthosilicates, such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), and pyrolytic silica, such as… (Available from Evonik) (Available from Cabot) and (Available from DMS), precipitated silica, for example and 340 (available from Evonik), aqueous colloidal suspensions of alkali metal silicates such as potassium silicate and sodium silicate, and silica, for example, by EIdu Pont de Nemours under the trade name Sold or sold by Evonik under the trade name Those for sale; preferably silicates, pyrolytic silica, precipitated silica, alkali metal silicates and colloidal silica.

[0187] The synthetic mixture contains at least one source of alumina. Suitable sources of alumina for this method include aluminum salts, particularly water-soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, alkali metal aluminates such as sodium aluminate, and aluminum alkoxylates such as isopropyl alumina, and 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 alkoxylates such as aluminum isopropyl aluminate, or aluminum metal, such as aluminum flakes.

[0188] In addition to the sources of Si and Al mentioned above, sources containing both Si and Al elements can be used, such as 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, or other macroporous to mesoporous zeolites.

[0189] The synthetic mixture can have a Si / Al molar ratio of 5 to 50, for example 5 to 40, or 30, especially 5 to less than 30, or 5 to 20, for example 5 or 10.

[0190] The synthetic mixture used to prepare RTH framework type zeolites contains fluoride ions (F) at an F / Si molar ratio of less than 0.1, for example, 0 to less than 0.1, or 0 to 0.05, or 0 to 0.01, for example, 0. In particular, the synthetic mixture used to prepare RTH framework type zeolites is substantially free of fluoride ions (F). This means that no significant amount of fluoride ion source is added to the synthetic mixture, for example, the synthetic mixture has an F / Si molar ratio of less than 0.1, especially less than 0.05, for example, less than 0.01 or even less than 0.005, for example, 0. The fluoride ions (F), when present, can be derived from any compound capable of releasing fluoride ions in the molecular sieve synthetic mixture, such as hydrogen fluoride (HF); salts containing one or more fluoride ions, such as metal fluorides, preferably wherein the metal is sodium, potassium, calcium, magnesium, strontium, or barium; ammonium fluoride (NH4F); and ammonium difluoride (NH4HF2). Small amounts of fluoride ions (F) may also be present as impurities, for example, in sources of optional alkali metal or alkaline earth metal cations (M).

[0191] The synthetic mixture may optionally contain at least one source of halide ions (W) different from fluoride ions, which may be selected from chlorides, bromides, or iodides, such as chlorides. The source of halide ions (W) can be any compound capable of releasing halide ions in the molecular sieve synthetic mixture. Non-limiting examples of halide ion sources include 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 halides; or tetraalkyl ammonium halides, such as tetramethyl ammonium halide or tetraethyl ammonium halide. The halide ions (W) may be present at a W / Si molar ratio of 0 to 1.0, for example, 0 to 0.5, such as 0.2 or 0.3. Alternatively, the synthetic mixture may be substantially free of halide ions (W).

[0192] Optionally, the synthetic mixture may also contain at least one source of hydroxide ions (OH). For example, hydroxide ions may be present as counterions to the structure-directing agent (Q), 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; for example, from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more generally from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most commonly from sodium hydroxide and / or potassium hydroxide. The synthetic mixture may contain a hydroxide ion source at an OH / Si molar ratio of 0 to 2.0, for example 0 to 1.5, or 0.1 to 1.5, for example 0.2 to 1.3, or 0.3 to 1.0, for example 0.4, 0.5, or 0.6 to 1.4, 1.2, or 1.0. Alternatively, the synthetic mixture may not contain a hydroxide ion source.

[0193] The synthetic mixture also contains a source of one or more alkali metal or alkaline earth metal cations (M). If present, M is preferably selected from sodium, potassium, lithium, rubidium, calcium, magnesium, and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. The sodium source, when present, can be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or sodium salts such as NaCl, NaBr, or sodium nitrate. The potassium source, when present, can be potassium hydroxide, potassium aluminate, potassium silicate, or potassium salts such as KCl or KBr or potassium nitrate. The lithium source, when present, can be lithium hydroxide or lithium salts such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. The rubidium source, when present, can be rubidium hydroxide or rubidium salts such as RbCl, RbBr, RBI, or rubidium nitrate. The calcium source, when present, can be, for example, calcium hydroxide. The magnesium source, when present, can be, for example, magnesium hydroxide. The alkali metal or alkaline earth metal cation M may also be present in one or more silica or alumina sources, such as sodium aluminate, potassium tetraborate, and / or sodium silicate. The synthetic mixture may contain the alkali metal or alkaline earth metal cation (M) source at an M / Si molar ratio of 0.1 to 2.0, for example 0.1 to 1.5, for example 0.15 to 1.0, for example 0.15, 0.2, or 0.3 to 1.0 or 0.7.

[0194] Synthesis can be carried out with or without additional nucleating seeds. If nucleating seeds are added to the synthesis mixture, these seeds may have the same or different structures as RTH framework-type molecular sieves, such as RTH zeolites from previous (same or different) synthesis, and may suitably be present in amounts from about 0.01 ppm to about 10,000 ppm by weight based on the synthesis mixture, for example, from about 100 ppm to about 5,000 ppm by weight based on the synthesis mixture.

[0195] The synthetic mixture typically contains water at an H₂O / Si molar ratio of 1 to 100, for example, 2 to 80, such as at least 10, 20, 30, or 40 and at most 80 or 70, such as 40-70. Depending on the nature of the components in the base mixture, the amount of solvent in the base mixture (e.g., water from a hydroxide solution, and optionally methanol and ethanol obtained from the hydrolysis of a silica source) can be removed to achieve the desired solvent-to-Si molar ratio in the synthetic mixture. Suitable methods for reducing the solvent content may include evaporation in a static or flowing atmosphere, such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. When excessive water is removed in the solvent removal process, 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.

[0196] Carbon in the form of CH2 can be present in various sources of those components used to prepare RTH zeolites, such as tetravalent element sources (silicon dioxide sources) or trivalent element sources (alumina sources), and can be introduced into the RTH zeolite framework as bridging atoms. After SDA has been removed, nitrogen atoms can be introduced into the RTH zeolite framework as bridging atoms.

[0197] In one or more aspects, the synthetic mixture after solvent adjustment (e.g., where the desired water-to-silica ratio is achieved) can be mixed mechanically, such as by stirring or high-shear blending, to ensure proper homogenization of the base mixture, for example using dual asymmetric centrifugal mixing (e.g., FlackTek Speedmixer) at a mixing speed of 1000 to 3000 rpm (e.g., 2000 rpm).

[0198] The synthetic mixture is then subjected to crystallization conditions suitable for forming RTH framework-type molecular sieves. Crystallization of the RTH molecular sieves can occur under static or stirred conditions in a suitable reactor vessel, such as a polypropylene tank or a convection furnace maintained at a suitable temperature. It is carried out in a lined or stainless steel autoclave.

[0199] The crystallization in step (b) of this method is typically carried out at a temperature of 100°C to 200°C, for example, 150°C to 170°C, for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be reduced. 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 (e.g., 1 to 12, 14, or 16 days, or 1 to 7 days). The crystallization time can be determined by methods known in the art, for example, by sampling the synthetic mixture at different times and determining the yield of the precipitated solids and the X-ray crystallinity. Unless otherwise stated, the measured temperature is the temperature of the environment surrounding the material being heated, such as the temperature of the atmosphere in which the material is heated.

[0200] Typically, RTH framework-type molecular sieves are formed as a solution and can be recovered using standard methods such as centrifugation or filtration. Separated RTH molecular sieves can also be washed, recovered by centrifugation or filtration, and dried.

[0201] The molecular sieves described herein, when used as adsorbents or catalysts in organic compound conversion processes, can be at least partially dehydrated (e.g., dried). This can be achieved by heating to temperatures ranging from 80°C to 500°C, for example from 90°C to 370°C, in an atmosphere such as air, nitrogen, etc., and at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure for 30 minutes to 48 hours. 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 achieve sufficient dehydration.

[0202] 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 virgin RTH zeolite recovered from step (c) can be heat-treated or otherwise treated to remove some or all of the SDA introduced into the pores during synthesis. Heat treatment (e.g., calcination) of the virgin RTH zeolite typically involves exposing the material in a furnace to a high temperature sufficient to remove some or all of the SDA in an atmosphere selected from air, nitrogen, ozone, or mixtures thereof. While pressures below atmospheric pressure can be used for heat treatment, atmospheric pressure is preferred for convenience. 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 ambient temperature surrounding the sample. Heat treatment (e.g., calcination) can be carried out in a box furnace in dry air, which has been exposed to a drying tube containing a desiccant for removing moisture from the air. This heating typically involves calcination for at least 1 minute to a period not exceeding 1 day or at most several days. The heating can be carried out first in a nitrogen atmosphere, and then the atmosphere can be switched to air and / or ozone.

[0203] RTH framework-type molecular sieves can also undergo ion exchange treatment, for example using aqueous solutions of 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 obtaining the molecular sieve in acid form. To the desired extent, the initial cations used to prepare the virgin material, such as alkali metal cations, can be replaced by other cations through ion exchange. Preferred cations for replacement may include hydrogen ions, hydrogen precursors such as ammonium ions, and mixtures thereof. The ion exchange step can be performed after drying to prepare the virgin molecular sieve. The ion exchange step can be performed before or after the calcination step.

[0204] RTH framework type molecular sieves can also undergo other treatments, such as steam treatment and / or solvent washing. These treatments are well known to those skilled in the art and are used to improve the desired properties of the molecular sieves.

[0205] As described in WO2001 / 044109, the aluminosilicate molecular sieve of the RTH framework type is characterized by an X-ray diffraction pattern, and the full text of this document is incorporated herein by reference. More particularly, the calcined form of the RTH aluminosilicate has a powder X-ray diffraction pattern including the characteristic peaks shown in Table 7, represented by °2θ and d-spacing values, where the d-spacing values have a deviation measured based on the corresponding deviation of ±0.20 °2θ when converted to the corresponding d-spacing values using Bragg's law:

[0206] Table 7

[0207]

[0208] The XRD pattern with the XRD peaks described herein uses Cu(K α ) radiation.

[0209] In a further embodiment, the present invention relates to an aluminosilicate molecular sieve of the RTH framework type obtainable (or obtained) by the method of the fourth aspect described herein.

[0210] The fifth aspect of the present invention relates to an aluminosilicate molecular sieve of the RTH framework type having within its pore structure the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridin-1-ium cation of formula I as defined above. The RTH zeolite can be represented by the molecular formula of formula VII:

[0211] (n)Q:(m)Al2O3:SiO2 (formula VII),

[0212] where 0 ≤ n ≤ 0.2, 0.01 < m ≤ 0.10, and Q is the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridin-1-ium cation of formula I. Formula VII represents the framework of a typical aluminosilicate RTH zeolite having a structure-directing agent (Q) within its pore structure, but this does not mean the only representation of the material. The RTH zeolite material may contain impurities, which are not counted in formula VII. Additionally, formula VII does not include protons and charge-compensating ions that may be present in the RTH zeolite material.

[0213] The variable m represents the molar ratio between Al2O3 and SiO2 in formula VII. For example, when m is 0.10, the molar ratio between Al2O3 and SiO2 is 10, and the Si / Al molar ratio is 5. m can vary within the range of 0.01 to 0.1, such as 0.0125 to 0.1, such as 0.025 to 0.1. The molar ratio between Si and Al can be within the range of 5 to 50, such as 5 to 40 or 30, especially 5 to less than 30, such as 5 to 20, or even 5 to 15, such as 5 to 10, or even 5 to less than 10.

[0214] The variable n represents the molar ratio between Q and SiO2 in formula VII. For example, when n is 0.1, the molar ratio between Q and SiO2 is 0.1. The molar ratio between Q and SiO2 can range from 0 to 0.2, such as 0.02 to 0.1, such as 0.03 to 0.06.

[0215] The sixth aspect of the present invention relates to a silicoaluminate molecular sieve of the RTH framework type, which has a particularly low Si / Al molar ratio, especially a Si / Al molar ratio less than 10, such as 5 to less than 10, such as 7 or 8. Such a silicoaluminate molecular sieve of the RTH framework type can be represented by the following formula VIII:

[0216] (m)Al2O3:SiO2 (Formula VIII),

[0217] where 0.05 < m ≤ 0.10. The variable m represents the molar ratio relationship between Al2O3 and SiO2 in formula VIII. For example, when m is 0.1, the molar ratio between SiO2 and Al2O3 is 10, and the Si / Al molar ratio is 5. The oxygen atoms in formula VIII can be replaced by carbon atoms (for example, in the form of CH2), which can be derived from the sources of the components used to prepare the as-made RTH zeolite. The oxygen atoms in formula VIII can also be replaced by nitrogen atoms, for example, after the SDA has been removed. Formula VIII can represent the framework of a typical calcined RTH zeolite, but this does not mean the only representation of the RTH zeolite. After suitable treatment to remove the SDA and impurities, the RTH zeolite may contain SDA and / or impurities, which are not included in formula VIII. In addition, formula VIII does not include the protons and charge compensation ions that may be present in the calcined form of the RTH zeolite.

[0218] Applications of RTH framework-type aluminosilicate molecular sieves

[0219] The silicoaluminate molecular sieve of the RTH framework type obtained by the method described in the fourth aspect of the present invention (where part or all of the SDA has been removed) or as defined in the fifth and sixth aspects of the present invention can be used as an adsorbent, or as a catalyst or catalyst support in a variety of hydrocarbon conversion processes, such as the conversion of organic compounds to conversion products.

[0220] Aluminosilicate RTH zeolite materials (in which some or all of the SDA has been removed) can be used as adsorbents, for example, to separate at least one component from a mixture of multiple components with different adsorption characteristics for the material in the gas or liquid phase. Thus, at least one component can be partially or substantially completely separated from a mixture of multiple components with different adsorption characteristics for the aluminosilicate RTH zeolite material by contacting the mixture with the RTH material to selectively adsorb one component. 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 can be contacted with an adsorbent comprising the aluminosilicate RTH zeolite of the present invention under effective adsorption conditions, thereby forming an adsorption product and an effluent product. One or more desired components can be recovered from the adsorption product or the effluent product.

[0221] Aluminosilicate RTH zeolites (with some or all of SDA removed) can also be used as catalysts for a wide variety of organic conversion processes. Examples of chemical conversion processes effectively catalyzed by the aluminosilicate RTH zeolites described herein (alone or in combination with one or more other catalytically active substances, including combinations with other crystalline catalysts) include those processes that require catalysts with acid activity. Examples of organic conversion processes that can be catalyzed by the aluminosilicate RTH zeolites described herein include cracking, hydrocracking, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, oligomerization, methanol to olefin conversion, deNOx application, and combinations thereof. The conversion of hydrocarbon feedstocks can be carried out in any convenient mode, such as in fluidized bed, moving bed, or fixed bed reactors, depending on the desired process type.

[0222] Aluminosilicate RTH zeolites can be formulated into product compositions by combining them with other materials, such as binders and / or matrix materials, which provide additional hardness to the final product. These other materials can be inert or catalytically active.

[0223] For example, it may be desirable to combine aluminosilicate RTH zeolites as described in the fifth or sixth aspect of the invention, or obtainable by the method described in the fourth aspect, with another material that can withstand the temperatures and other conditions used during use. Such materials include synthetic or natural zeolites, and inorganic materials such as clay, silica, and / or metal oxides such as alumina, or 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 a resistant material in conjunction with aluminosilicate RTH zeolites, i.e., in combination with or during the synthesis of pristine aluminosilicate RTH zeolites (where the crystals are active), tends to alter the conversion rate and / or catalyst selectivity in certain organic conversion processes. Inactive resistant materials suitably act as diluents to control the conversion amount in a given process, thereby obtaining the product in an economical and orderly manner without using other means of controlling the reaction rate. These materials may be incorporated into natural clays, such as bentonite and kaolin, to improve the crushing strength of the product under commercial operating conditions. The inactive, resistant materials, such as clay and oxides, act as a binder for the catalyst. Catalysts with good crushing strength are beneficial because it is desirable to prevent the catalyst from breaking into powdery material in commercial applications.

[0224] Available natural clays include the montmorillonite and kaolinite families, which include sub-bentonite, and kaolinite commonly known as Dixie, McNamee, Georgia, and Florida clays, or other clays whose main mineral components are halloysite, kaolinite, dickite, perlite, or vermicular clay. These clays can be used in their original, unprocessed state, or after calcination, acid treatment, or chemical modification. Binders that can be used in composites with aluminosilicate RTH zeolites 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.

[0225] In addition to the materials mentioned above, aluminosilicate RTH zeolites 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.

[0226] These binder materials are resistant to temperature and other conditions, such as mechanical grinding, which occurs in various hydrocarbon separation processes. Therefore, aluminosilicate RTH zeolites can be used in extrusion form with binders. They are typically combined by forming pellets, spheres, or extrusions. Extrusions are typically formed by extruding molecular sieves optionally in the presence of a binder, followed by drying and calcining the resulting extrusion. Further processing, such as steam treatment and / or ion exchange, can be performed as needed. Molecular sieves can optionally be combined with materials having a thickness of at least 100 μm. 2 / g of surface area adhesive bond, for example at least 200m 2 / g, optionally at least 300m 2 / g.

[0227] The relative ratio of molecular sieves and inorganic oxide matrix can vary over a wide range, with the molecular sieve content ranging from about 1 to 100% by weight, especially when the composite is prepared in the form of an extrusion, the content is more typically about 2 to 95% by weight of the composite, optionally about 20 to 90% by weight.

[0228] Aluminosilicate RTH zeolites can also be closely incorporated with hydrogenated components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals like platinum or palladium, where they are intended to perform hydrogenation-dehydrogenation functions. These hydrogenated components can be incorporated into the composition by one or more of the following methods: co-crystallization; exchange into the composition to include a Group IIIA element, such as aluminum, in the structure; or close physical mixing. These components can also be impregnated into or onto the aluminosilicate RTH zeolite, for example, by treating a molecular sieve with ions containing hydride metals. For example, in the case of platinum, suitable platinum compounds include chloroplatinic acid, platinum(II) chloride, and various compounds containing platinumamine complexes. Combinations of metals and introduction methods can also be used.

[0229] Those skilled in the art will understand that aluminosilicate RTH zeolites, as described in the fifth or sixth aspect of the invention or obtainable by the method described in the fourth aspect, 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 crystalline materials coexisting with aluminosilicate RTH zeolites are quartz, mordenite, cristobalite, zeolite P, and / or ANA framework-type molecular sieves. Aluminosilicate RTH zeolites are preferably substantially free of impurities. The term “substantially free of impurities” (or, as another expression, “substantially pure”) as used herein means that the aluminosilicate RTH 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 these impurities (or “non-RTH materials”), wherein the weight percentage (wt%) value is based on the total weight of the impurities and the pure aluminosilicate RTH zeolite. The amount of impurities can be appropriately determined by powder XRD, rotating electron diffraction and / or SEM / TEM (e.g., different crystal morphologies).

[0230] The aluminosilicate RTH zeolite described herein is 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 represent a regular and / or ordered molecular arrangement with an identifiable crystal lattice. For example, aluminosilicate RTH 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 a majority of the weight (greater than 50% by weight) of the sample of the solid material is crystalline, and the remainder of the sample is amorphous. In one or more aspects, the substantially crystalline sample has at least 95% crystallinity (e.g., 5% amorphous form), at least 96% crystallinity (e.g., 4% amorphous form), at least 97% crystallinity (e.g., 3% amorphous form), at least 98% crystallinity (e.g., about 2% amorphous form), at least 99% crystallinity (e.g., 1% amorphous form), and 100% crystallinity (e.g., 0% amorphous form).

[0231] Various aspects of this disclosure are described in more detail with reference to 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 obtain substantially the same results. Example

[0232] The present invention will be further described below, but this does not limit the scope of the invention.

[0233] In these embodiments, X-ray diffraction data of the prepared raw and calcined materials were recorded in continuous mode using Cu Kα radiation and a Bragg-Bentano geometry with a Vantec 500 detector on an X-ray powder diffractometer (Bruker DaVinci D8 Discoveryinstrument), within a 2θ range of 4 to 36°. The interplanar spacing d-spacing was calculated in angstroms, and the relative intensity I / I of the lines was also calculated. o This is the ratio of the peak intensity above the background to the intensity of the strongest line. These intensities are uncorrected for Lorentz and polarization effects. The relative peak area intensity I / I(o) of the diffraction peak positions in 2θ is determined using the MDI Jade peak search algorithm, where Io is the intensity of the strongest line above the background. It should be understood that diffraction data listed as single lines may consist of multiple overlapping lines, which may appear as split or partially split lines under certain conditions, such as differences in crystallographic variations. Typically, crystallographic variations can include slight changes in cell parameters and / or crystal symmetry, without structural invariance. These slight effects, including variations in relative intensity, can also occur due to differences in cation content, framework composition, the nature and degree of pore filling, crystal grain size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0234] Scanning electron microscopy (SEM) images of the prepared raw material were obtained using a Hitachi 4800 scanning electron microscope. SEM images are used to help evaluate product purity. The presence of distinctly different crystal morphologies in the SEM images can indicate impurities in other crystalline forms. This approximate analysis can be particularly useful in confirming the formation of small amounts of crystalline impurities that cannot be confirmed by the product's XRD pattern.

[0235] The following tests were performed on the samples after ion exchange and calcination. Each sample underwent ion exchange and calcination as follows: the original sample was washed twice with 1M ammonium nitrate solution, and then calcined at 500°C for 16 hours.

[0236] The total BET surface area (SBET) of the material was determined by the BET method described by S. Brunauer, PHEmmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309, the contents of which are incorporated herein by reference, wherein nitrogen adsorption-desorption was performed at liquid nitrogen temperature.

[0237] The micropore volume of a material can be determined using methods known in the relevant field. For example, the micropore volume of a material can be measured using nitrogen physical adsorption, and the data can be analyzed using the t-plot method described in Lippens, BC, et al., “Studies on pore system in catalysts: V. The t method”, J. Catal., 4, 319 (1965), which describes a method for measuring micropore volume and is hereby cited and incorporated herein by reference.

[0238] The α value is a measure of the cracking activity of a catalyst, and can be found 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 test conditions used herein included a constant temperature of 538 °C and variable flow rates, as detailed in the Journal of Catalysis, Vol. 61, p. 395.

[0239] Example 1 - Synthesis of 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium hydroxide

[0240] In a 500 mL round-bottom flask, 25.0 g of 6,7-dihydro-5H-cyclopenta[b]pyridine was dissolved in 200 mL of acetone. Under ambient conditions, 41.76 g of iodomethane was then slowly added dropwise to the flask via a dropping funnel. The next day, diethyl ether was added to precipitate any undissolved solids. The solid was then recovered by filtration, washed with diethyl ether, and dried. The yield of the recovered product was 52 g. The purity of the product was confirmed by 1H and 13C NMR.

[0241] The halide salt of 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium was then dissolved in water and added to a two-fold excess of Dowex LC NG hydroxide exchange resin for ion exchange to its hydroxide form. The resin was then removed by filtration, and the product was washed with deionized water to remove it from the resin. The aqueous fractions were then combined and concentrated under reduced pressure at approximately 60°C. The concentration of the aqueous solution was determined to be 7.4% by weight by titration with a standard solution of 0.1 M HCl.

[0242] Example 2 - Synthesis of EMM-64

[0243] The molar ratios and conditions used in the synthesis of Examples 2.01 to 2.21 and the resulting products are described in detail below and summarized in Table 8.

[0244] Example 2.01 - Synthesis of EMM-64

[0245] EMM-64 was first observed to be synthesized as follows: A 10-day synthesis was carried out at 150°C in a rotating 1.5 mL stainless steel reactor from a synthetic mixture having the following composition expressed in molar ratios: H₂O / Si = 4, Q / Si = 0.50, OH / Si = 0.50, HF / Si = 0.50, wherein 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium hydroxide prepared in Example 1 was used as the structure directing agent (Q) (7.4 wt% solution). The silica source was tetramethyl orthosilicate (TMOS, >99 wt%). HF was in the form of a 15 wt% solution.

[0246] The product was separated by centrifugation, then suspended in deionized water, and centrifuged again. This process was repeated three times, after which the product was dried at 90°C. The raw material was then calcined to 600°C in a box furnace according to the following procedure: The sample was exposed to flowing nitrogen at room temperature for 2 hours, then increased from room temperature to 400°C over 2 hours while maintaining a nitrogen flow. The temperature was then held at 400°C for 15 minutes, after which the atmosphere was switched from flowing nitrogen to flowing dry air. Subsequently, the temperature was increased from 400°C to 600°C over 1 hour. This temperature was held at 600°C for 2 hours, after which the box furnace was cooled.

[0247] XRD analysis of the raw and calcined materials revealed that these materials possess unique powder XRD patterns that cannot be matched with any known zeolite, and were identified as pure EMM-64 products prepared in both raw and calcined forms. Figure 1 The powder XRD pattern shows the original and calcined materials. Figure 2 Showing SEM images of the original product.

[0248] Example 2.02 - Large-scale synthesis of EMM-64

[0249] This example is a larger-scale re-preparation of Example 2.01, in 10 mL The reaction was carried out in a reactor. 17.4 g of 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium hydroxide (7.4 wt% solution) was added to 2.6 g of TMOS (>99 wt%). The mixture was placed on a stirring plate and stirred for 1 hour, then placed in a vacuum oven at approximately 50°C. The reactor was kept in the vacuum oven and weighed periodically until 16.15 g of water evaporated. The container was then removed from the vacuum oven, and 0.262 g of water and 1.14 g of HF (15 wt% solution) were added to the reactor. The Teflon reactor was then placed in a metal shell and heated at 150°C in a tumbling oven (approximately 45 rpm) for 14 days. After 14 days, the product was discharged from the reactor and collected by centrifugation and washing three times with distilled water (200 mL). The product was dried in a ventilated drying oven at 90°C. The XRD patterns of the raw and calcined materials show that the product is pure EMM-64.

[0250] Examples 2.03 to 2.05 - Synthesis of EMM-64 at different H2O / Si molar ratios

[0251] These examples were conducted under similar conditions to Example 2.02, except that the H2O / Si molar ratios were changed to 20, 30, and 50, respectively. Pure EMM-64 was obtained after heating at 150°C for 14 days in each experiment, which confirmed its XRD pattern.

[0252] Examples 2.06 to 2.11 - Synthesis of EMM-64 at 130°C with different H2O / Si molar ratios

[0253] These examples were conducted under similar conditions to Example 2.02, except that the temperature was 130°C and the H2O / Si molar ratio varied from 4 to 50. Pure EMM-64 was obtained after heating at 150°C for 14 days in each experiment, using 3.6 g of TMOS reactant.

[0254] Examples 2.08, 2.06, and 2.09 yielded pure EMM-64 at H2O / Si molar ratios of 7, 10, and 20, which was confirmed by their XRD patterns. At a low H2O / Si molar ratio of 4, Example 2.07 yielded mostly amorphous product and a small amount of EMM-64 after 27 days at 130°C. At higher H2O / Si molar ratios of 30 and 50, Examples 2.10 and 2.11 yielded EMM-64 and a small amount of amorphous material, respectively, after 27 days at 130°C.

[0255] Figure 3SEM images of the prepared in-state product of Example 2.06 are shown. Tables 9 and 10 below show a list of the peaks and their intensities for the calcined form and the prepared in-state EMM-64 product of Example 2.06. The powder diffraction data of the prepared in-state and calcined EMM-64 products can be represented as tetragonal space group I 41 2 2, with unit cell size... and We also analyzed the powder diffraction data of EMM-64 material, resolved its structure by powder XRD and using the FOCUS algorithm, and showed that the material has a 3D 8-ring channel system and a chiral framework.

[0256] Examples 2.12 to 2.15 – Synthesis of EMM-64 at 150 °C with a lower H2O / Si molar ratio

[0257] These examples were conducted at 150°C under similar conditions to Example 2.02, except that the H2O / Si molar ratio was in the range of 1 to 4. Pure EMM-64 was obtained after heating at 150°C for 5–7 days in each experiment, which confirmed its XRD pattern.

[0258] Figure 4 SEM images of the original product prepared in Example 2.12 are shown. The 4x symmetry of the crystals is evident. Adsorption tests were performed on a sample of the product from Example 2.12. The micropore volume (Vmicro) is 0.13 cc / g, and the uptake of n-hexane is very slow, reaching only 4.6 mg / g.

[0259] Examples 2.16 to 2.21 - Synthesis of EMM-64 in the presence of an aluminum source at different Si / Al molar ratios.

[0260] These examples were carried out under similar conditions to Example 2.02 at 150°C and an H2O / Si molar ratio of 4, except that an aluminum source was present and the Si / Al molar ratio was changed to 100, 30, and 20. Two different aluminum sources were used in these examples: aluminum nitrate (15% by weight solution) was used in Examples 2.16-2.18, and MS-25 amorphous silica-alumina (65.5% silica / 22% alumina) was used in Examples 2.19-2.21. Pure EMM-64 was obtained after heating at 150°C for 6-7 days in each example, which was confirmed by its XRD pattern.

[0261] Figure 5 SEM images of the original products prepared in Examples 2.16, 2.17, and 2.18 are shown. It can be seen that increasing the amount of aluminum has a double effect: with increasing Al content, the crystallites become smaller and less faceted, growing more inward. Figure 6 Examples 2.16, 2.17 and 2.18 show how increasing aluminum content leads to broader diffraction peaks in powder XRD, while individual crystallites become smaller.

[0262] Table 8

[0263]

[0264] Table 9

[0265]

[0266] Table 10

[0267]

[0268] Example 3 - Synthesis of EMM-65

[0269] The molar ratios and conditions used in the synthesis of Examples 3.01 to 3.05 and the resulting products are described in detail below and summarized in Table 11.

[0270] Example 3.01 - Synthesis of EMM-65

[0271] EMM-65 was first observed to be synthesized as follows: A synthesis mixture having the following molar ratios was carried out for 7 days at 160°C in a rotating 1.5 mL stainless steel reactor from a synthesis mixture: H₂O / Si = 36, Q / Si = 0.20, Na / Si = 0.10, OH / Si = 0.30, and Si / B = 20, wherein 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium hydroxide prepared in Example 1 was used as the structure directing agent (Q) (7.4 wt% solution). The silica source was Aerodisp W7330N (30 wt% colloidal silica suspension). The boron source was boric acid (3.047 wt% solution). The M source was NaOH (10 wt% solution).

[0272] The product was separated by centrifugation, then suspended in deionized water, and centrifuged again. This process was repeated three times, after which the product was dried at 90°C. The raw material was then calcined to 600°C in a box furnace according to the following procedure: The sample was exposed to flowing nitrogen at room temperature for 2 hours, then increased from room temperature to 400°C over 2 hours while maintaining a nitrogen flow. The temperature was then held at 400°C for 15 minutes, after which the atmosphere was switched from flowing nitrogen to flowing dry air. Subsequently, the temperature was increased from 400°C to 600°C over 1 hour. This temperature was held at 600°C for 2 hours, after which the box furnace was cooled.

[0273] XRD analysis of the prepared raw and calcined materials revealed unique powder XRD patterns that could not be matched with any known zeolite, and these were identified as pure prepared raw and calcined EMM-65 products. Layered phase impurities were observed as a peak at approximately 4.5°2θ. Upon calcination, this feature was retained but lost intensity and shifted to 5.1°2θ. The position of this peak corresponds to the presence of kenyaite. Figure 8 The image shows a SEM image of the original product. Needle-like or strip-like structures are derived from EMM-65, while plate-like structures are derived from layered phase impurities.

[0274] Example 3.02 - Large-scale synthesis of EMM-65 (45 mL)

[0275] This example is a larger-scale re-preparation of Example 3.01, carried out in a 45 mL PTFE-lined stainless steel Parr autoclave. 6.7 g of Aerodisp W 7330N, 13.7 g of 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium hydroxide (7.4 wt% solution), 3 g of boric acid solution (3.047 wt%), 1.34 g of NaOH solution (10 wt%), and 0.26 g of deionized water were added and mixed to form a homogeneous suspension. The mixture was then sealed in the autoclave reactor, which was placed in a convection furnace rack and heated at 160 °C under rotating conditions (approximately 40 rpm) for 7 days. After washing and filtering with approximately 250 mL of deionized water, the solid product was dried overnight in an oven at 90 °C to obtain 2.2 g of dried product.

[0276] Powder XRD patterns of raw and calcined materials are prepared as follows: Figure 9 As shown, this indicates that the product is pure EMM-65. Tables 12 and 13 below show the peak positions and intensities of the calcination form of Example 3.02 and the powder XRD patterns of the prepared pristine EMM-65 product. Figure 10 The SEM image shows the original EMM-65 product, which consists of needle-like or strip-like structures. The SEM image also shows the absence of plate-like structures as observed in small-scale example 3.01.

[0277] Example 3.03: Large-scale synthesis of EMM-65 (125 mL)

[0278] This example is a larger-scale re-preparation of Example 3.02, carried out in a 125 mL steel Parr autoclave lined with PTFE. The synthesis used 18.8 g of Aerodisp W 7330N. After heating at 160 °C for 7 days, pure EMM-65 was obtained, which was confirmed by its XRD pattern. Elemental analysis by inductively coupled plasma (ICP) revealed that the calcined product had a Si / B atomic ratio of 22.4 and a Na / Si atomic ratio of 0.005.

[0279] Example 3.04 - Large-scale synthesis of EMM-65 (300 mL)

[0280] This experiment was a large-scale re-preparation of Example 3.02, carried out in a 300 mL headspace-stirred steel Parr autoclave. The synthesis used 64.4 g of Aerodisp W 7330N and 0.19 g of the product from Example 3.03 as seed. After heating at 160 °C for 8 days, pure EMM-65 was obtained, which confirmed the XRD pattern of the original product, as shown in the figure. Figure 11 As shown. The powder XRD pattern is consistent with... Figure 7 and Figure 9 The steeper profile is due to the thicker crystal size. Figure 12 SEM images of the prepared in-state EMM-65 product are shown. Powder diffraction data for both in-state and calcined EMM-65 products can be represented as orthorhombic space group Pmmn2, where the unit cell size... and Electron diffraction analysis of the EMM-65 product sample revealed that it possesses a 1D 12-ring channel system with a pore size of [missing information]. Figure 13 Showing the projection of EMM-65 along its 12-ring pores.

[0281] The raw material was calcined at 500°C for 16 hours, followed by ammonium ion exchange with 1M ammonium nitrate solution in a batch system, and then calcined again at 500°C for 16 hours. The BET surface area (S) of this material was determined. BET ) is 387m 2 / g, its micropore volume (V micro The concentration is 0.13 cc / g.

[0282] Example 3.05 - Synthesis of EMM-65 using KOH as the M source

[0283] This experiment was conducted under similar conditions to Example 3.02, except that KOH was used instead of NaOH as the M source, and 0.0145 g of the product from Example 3.03 was added as a seed. This synthesis used 4.8 g of Aerodisp W 7330N. Pure EMM-65 was obtained after heating at 160 °C for 12 days, which confirmed its XRD pattern. The powder XRD pattern exhibited a wider feature than the previous sample due to the thicker crystallites.

[0284] Table 11

[0285]

[0286] Table 12

[0287]

[0288] Table 13

[0289]

[0290] Example 3.06 - Preparation of EMM-65 for Aluminum Exchange

[0291] A portion of the product from Example 3.04, which underwent ammonium exchange and calcination, was heated overnight at 80°C in a 1M aluminum nitrate solution to exchange framework B with Al. The product was then dried at 100°C and calcined at 500°C for 16 hours.

[0292] The Si / Al atomic ratio of the calcined sample is approximately 37, as determined by EDX. The α value of the calcined sample is 5, and its BET surface area (S) is... BET ) is 350m 2 / g, and its micropore volume (V micro The adsorption rate was 0.14 cc / g. The adsorption of n-hexane, 2,3-dimethylbutane (2,3-DMB), and 1,3,5-trimethylbenzene on a calcined sample was detected. The material was placed in a nitrogen stream, and hydrocarbons were introduced via a distributor to saturate the nitrogen stream, and the hydrocarbon adsorption was detected. Each hydrocarbon was adsorbed at different temperatures: n-hexane at 90 °C; 2,3-DMB at 120 °C; and 1,3,5-trimethylbenzene at 100 °C. The adsorption amount of n-hexane was 50.5 mg / g, 2,3-DMB was 45 mg / g, and 1,3,5-trimethylbenzene was 58 mg / g.

[0293] Example 4 - Synthesis of RTH zeolite

[0294] The starting materials, molar ratios and conditions used in the synthesis of Examples 4.01 to 4.11, as well as the resulting products, are detailed below and summarized in Table 14.

[0295] Example 4.01 - Synthesis of RTH zeolite

[0296] The following reagents were added in the following order to a 1.5 mL stainless steel reactor while stirring at approximately 200 rpm: 7.76 μl of distilled water, 324.5 μl of 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium hydroxide (7.4 wt% solution) as a structure-directing agent (Q), 74.54 μl of Ludox LS-30 (30 wt% colloidal silica suspension), 58.13 μl of NaOH (10 wt% solution), and 8.40 mg of Ultrastable Y (USY, Si / Al = 3). The resulting synthetic mixture had the following composition expressed in molar ratios: H₂O / Si = 45, Si / Al = 20, Q / Si = 0.30, OH / Si = 0.60, M / Si = 0.30. The synthetic mixture was stirred for approximately 2 hours and then placed in a rotary oven at approximately 45 rpm and heated at 160 °C for 7 days. The reaction mixture was cooled, the product was recovered by centrifugation, washed with distilled water, and centrifuged again. This process was repeated three times. The product was then dried in a ventilated drying oven at 90°C. The raw material was then calcined to 600°C in a box furnace according to the following procedure: The sample was exposed to flowing nitrogen at room temperature for 2 hours, and then the temperature was increased from room temperature to 400°C over 2 hours while maintaining a nitrogen flow. The temperature was then held at 400°C for 15 minutes, after which the atmosphere was switched from flowing nitrogen to flowing dry air. Subsequently, the temperature was increased from 400°C to 600°C over 1 hour. This temperature was held at 600°C for 2 hours, and then the box furnace was cooled.

[0297] XRD analysis of the calcined material showed that it possessed the powder XRD pattern characteristics of an aluminosilicate zeolite belonging to the RTH framework type. The material also contained a small amount of quartz.

[0298] Example 4.02 - Repeat Example 4.01 with a longer heating time of 28 days.

[0299] This example was carried out under similar conditions to Example 4.01, except that the synthesis mixture was heated for 28 days instead of 7 days. The resulting product was confirmed to be a mixture of RTH zeolite and quartz (approximately 50:50).

[0300] This result can be explained by the presence of excess silica in the synthetic mixture: a Si / Al molar ratio of 20, compared to 7 in the ideal composition of the RTH zeolite product, with two molecules of structure-directing agent (SDA) per cage, thus having two positive charges per cage. This excess silica can be amorphous, dissolved in the mother liquor, or crystallized as a silica-rich phase, such as quartz. It is not desirable to be bound by any theory, but it is assumed that initially most of the excess silica remains dissolved in the mother liquor, especially considering the high OH content (OH / Si = 0.6) of this synthetic mixture. However, over time, the dissolved silica can form quartz. This can also be facilitated by a decrease in OH content, as SDA can degrade and consume a portion of the said OH content over time.

[0301] Example 4.03 - Synthesis of RTH zeolite at a lower Si / Al molar ratio

[0302] This example was conducted under similar conditions to Example 4.02, except that the Si / Al molar ratio of the synthesized mixture was 10. The XRD pattern confirmed that the obtained product was RTH zeolite. This confirms the interpretation of the results obtained in Example 4.02.

[0303] Examples 4.04 to 4.06 - Synthesis of RTH zeolite using Georgia metakaolin as Al source

[0304] Example 4.04 was conducted under similar conditions to Example 4.03, but Georgia metakaolin was used as the Al source. Example 4.05 was conducted under similar conditions to Example 4.04, but a lower Si / Al molar ratio of 5 and a shorter heating time of 14 days were used. Example 4.06 was conducted under similar conditions to Example 4.05, but KOH was used instead of NaOH. The XRD pattern confirmed that the obtained product was RTH zeolite, possibly in combination with ANA framework-type zeolites.

[0305] Examples 4.07 to 4.08 - Synthesis of RTH zeolite using sodium aluminate as an Al source

[0306] Example 4.07 was carried out under similar conditions to Example 4.03, but sodium aluminate (NaAlO2, 8.86 wt% solution) was used as the Al source. Example 4.08 was carried out under similar conditions to Example 4.07, but at a lower temperature of 120°C and a lower NaOH / Si molar ratio of 0.15. The obtained product was confirmed to be RTH zeolite based on its XRD pattern.

[0307] Examples 4.09 to 4.11 - Alternative Examples of RTH Zeolite Synthesis

[0308] Example 4.09 was conducted following the experimental procedure of Example 4.01, but with the use of Aerodisp W7330N (30 wt% colloidal silica suspension) as the Si source and sodium aluminate (NaAlO2, 8.86 wt% solution) as the Al source, and a lower Si / Al molar ratio of 5. The product was confirmed to be RTH zeolite based on its XRD pattern.

[0309] Example 4.10 was carried out in a similar manner to Example 4.09, but with different H2O / Si, Si / Al, and NaOH / Si molar ratios as shown in Table 14, and in the presence of HCl. The XRD pattern confirmed that the resulting product was a mixture of RTH and ANA zeolites.

[0310] Example 4.11 was carried out in a similar manner to Examples 4.09 or 4.10, but at a lower temperature of 120°C, a longer heating time of 28 days, and with different molar ratios as shown in Table 14, in the presence of HCl. The XRD pattern confirmed that the obtained product was RTH zeolite.

[0311] Table 14

[0312]

[0313] *L = Ludox LS-30A, A = Aerodisp W 7330N, MK = Metakaolin, Y = Ultrastable Y, SA = Sodium aluminate.

[0314] Unrestricted by any theory, the inventors believe that the RTH zeolite product adsorbs two molecules of structure-directing agent (SDA) per RTH cavity. These molecules can be pi-stacks. The high charge density outside the framework necessitates a high negative charge on the framework, so that RTH can crystallize as a pure substance from the synthetic mixture, especially with a low Si / Al molar ratio, for example, less than 15, such as 10 or even 5. In the absence of adsorbed alkali metal cations, the ideal Si / Al ratio for two SDAs per cavity is 7. For a single charged cation per cavity, the ideal Si / Al ratio is 15.

[0315] Comparative Example 5 - Using 1-methyl-5,6,7,8-tetrahydroquinolinetonium hydroxide as a structure-directing agent

[0316] Example 3.02 was repeated, except that instead of 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium hydroxide, 1-methyl-5,6,7,8-tetrahydroquinolineonium hydroxide was used as the structure directing agent (Q). After heating at 160°C for 7 days, a mixture of SSZ-59 (SFN framework type) and quartz was obtained.

[0317] Although the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will understand that many different modifications, alterations, and variations can be made to the invention not specified herein. It will be apparent to those skilled in the art that when lower and upper limits of numerical values ​​are listed herein, a range from any lower limit to any upper limit is considered. Similarly, all numerical values ​​mentioned in the detailed description are also indicated by the word "about" modifying the specified value and take into account experimental error and variations that those skilled in the art would expect.

[0318] In the foregoing description, the entities or elements mentioned have known, obvious, or foreseeable equivalents, and these equivalents are also incorporated herein. The scope of the invention should be determined with reference to the claims and should be understood to cover any of these equivalents. It will also be apparent to the reader that the entities or features of the invention described herein as preferred, advantageous, convenient, etc., are optional and do not limit the scope of the independent claims. Furthermore, it should be understood that these optional entities or elements, while potentially beneficial in some embodiments of the invention, may not be ideal in other embodiments and therefore may be absent.

[0319] As an adjunct or alternative, the present invention relates to:

[0320] Implementation Scheme 1: The use of the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of Formula I as a structure directing agent in the preparation of zeolites:

[0321]

[0322] Implementation Scheme 2: The use described in Implementation Scheme 1, wherein the 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I is in the form of its hydroxide and / or halide, preferably in the form of its hydroxide, chloride, bromide, iodide or fluoride, more preferably in the form of its hydroxide or fluoride, and most preferably in the form of its hydroxide.

[0323] Implementation Scheme 3: The use described in Implementation Scheme 1 or 2, for preparing zeolites of the EMM-64, EMM-65 or aluminosilicate RTH framework type.

[0324] Implementation Scheme 4: A crystalline material called EMM-64, having, in calcined form, an X-ray diffraction pattern comprising at least 9 peaks selected from Table 1, preferably at least 10 peaks, more preferably at least 11 peaks, and most preferably all peaks.

[0325] Table 1

[0326] °2θ(±0.20) Relative intensity [100 x I / (Io)] 8.11 60-100 9.10 10-20 12.86 10-20 13.41 10-30 15.20 30-60 19.74 20-40 19.94 10-30 20.65 40-70 23.78 40-70 27.11 10-20 27.70 10-30 28.70 10-30

[0327] Implementation Scheme 5: The material described in Implementation Scheme 4 has the molecular formula of Formula II:

[0328] (m)X2O3:YO2 (Formula II),

[0329] Wherein 0 ≤ m ≤ 0.025, X is a trivalent element, and Y is a tetravalent element; in particular, X includes one or more of Al, B, Fe and Ga, preferably X includes Al and / or B, more preferably Al, and Y includes one or more of Si, Ge, Sn, Ti and Zr, preferably Y includes Si.

[0330] Implementation Scheme 6: A crystalline material called EMM-64, which, in its original state, has an X-ray diffraction pattern comprising at least 7 peaks, preferably at least 8 peaks, and more preferably all peaks selected from Table 3:

[0331] Table 3

[0332] °2θ(±0.20) Relative intensity [100 x I / (Io)] 8.08 20-40 15.20 10-30 19.54 30-60 19.94 10-30 20.56 50-80 23.79 60-100 27.12 10-30 27.69 20-40 28.50 20-40

[0333] Implementation Scheme 7: The material described in Implementation Scheme 6 has the molecular formula of Formula III:

[0334] (n)Q:(m)X2O3:YO2 (Formula III),

[0335] Where 0 ≤ n ≤ 0.2, 0 ≤ m ≤ 0.025, Q is the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I, X is a trivalent element, and Y is a tetravalent element.

[0336]

[0337] In particular, X includes one or more of Al, B, Fe and Ga, preferably X includes Al and / or B, more preferably Al, and Y includes one or more of Si, Ge, Sn, Ti and Zr, preferably Y includes Si.

[0338] Implementation Scheme 8: The crystalline material of any one of Implementation Schemes 4 to 7, having a framework defined by the connectivity of tetrahedral (T) atoms in the unit cell as shown in Table 2, wherein the tetrahedral (T) atoms are connected by bridging atoms:

[0339] Table 2

[0340]

[0341] Topologically equivalent atoms have the same "T-type" symbol at their positions.

[0342] b The size and number of the smallest rings at each angle of the T-atom (M.O'Keeffe and SHyde, Zeolite, 19, 370 (1997)).

[0343] Implementation Scheme 9: A method for preparing EMM-64 crystalline material according to any one of Implementation Schemes 4 to 8, comprising:

[0344] (a) Prepare a synthetic mixture comprising water, a source of an oxide of a tetravalent element (Y), optionally a source of an oxide of a trivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), and optionally a source of an alkali metal and / or alkaline earth metal element (M).

[0345] The structure-directing agent (Q) comprises the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I:

[0346] and

[0347] The synthetic mixture contains fluoride ions (F) at a molar ratio of at least 0.1 for F / Y;

[0348] (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 crystalline material;

[0349] (c) Recover at least a portion of the crystalline material from step (b); and

[0350] (d) Optionally, the crystalline material recovered in step (c) is treated to remove at least a portion of the structure-directing agent (Q).

[0351] Implementation Scheme 10: The method of Implementation Scheme 9, wherein the synthetic mixture has the following composition expressed in molar ratios:

[0352] molar ratio Typical range Preferred range More preferred range Y / X 10 to infinity 20-500 (if X exists) 20-100 (if X exists) Q / Y 0.01-1.0 0.05-1.0 0.1-0.8 F / Y 0.1-1.0 0.2-0.8 0.3-0.7 OH / Y 0-1.5 0.05-1.0 (if OH is present) 0.1-0.8 (if OH is present) M / Y 0-1.5 0.05-1.0 (if M exists) 0.1-0.8 (if M exists) H2O / Y 1-100 1-75 1-50 .

[0353] Implementation Scheme 11: A crystalline material called EMM-65, having, in calcined form, an X-ray diffraction pattern comprising at least 8 peaks selected from Table 4, preferably at least 9 peaks, more preferably at least 10 peaks, and most preferably all peaks.

[0354] Table 4

[0355] °2θ(±0.20) Relative intensity [100 x I / (Io)] 6.58 60-100 7.91 50-80 8.56 30-60 10.30 20-40 19.76 20-40 20.52 10-30 21.83 10-30 24.07 20-40 24.76 10-20 25.55 10-20 26.54 10-20 .

[0356] Implementation Scheme 12: The material described in Implementation Scheme 11 has the molecular formula of Formula IV:

[0357] (m)B2O3:SiO2 (Formula IV),

[0358] where 0.005 ≤ m ≤ 0.05.

[0359] Embodiment 13: A crystalline material designated EMM-65 having an X-ray diffraction pattern in as-made form comprising at least 18 peaks, preferably at least 19 peaks, more preferably at least 20 peaks, and most preferably all peaks selected from Table 6:

[0360] Table 6

[0361]

[0362]

[0363] Embodiment 14: The material of Embodiment 13 having a molecular formula of Formula V:

[0364] (n)Q:(m)B2O3:SiO2 (Formula V),

[0365] where 0 ≤ n ≤ 0.2, 0.005 < m ≤ 0.05, and Q is a 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridin-1-ium cation of Formula I:

[0366]

[0367] Embodiment 15: The crystalline material of any one of Embodiments 11 to 14 having a framework defined by the connectivity of tetrahedral (T) atoms in the unit cell as shown in Table 5 below, said tetrahedral (T) atoms being connected by bridging atoms:

[0368] Table 5

[0369]

[0370] The positions of topologically equivalent atoms have the same "T-type" symbol.

[0371] b The size and number of the smallest rings at each angle of the T-atoms (M. O’Keeffe and S.T. Hyde, Zeolites, 19, 370 (1997)).

[0372] Embodiment 16: A method for preparing the EMM-65 crystalline material according to any one of Embodiments 11 to 15, comprising:

[0373] (a) Preparing a synthetic mixture comprising water, a source of silica, a source of boron (B), a structure-directing agent (Q), optionally a source of hydroxyl (OH) ions, and optionally a source of an alkali metal and / or alkaline earth metal element (M),

[0374] The structure-directing agent (Q) comprises the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I:

[0375] and

[0376] The synthetic mixture contains fluoride ions (F) at an F / Si molar ratio of less than 0.1;

[0377] (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 crystalline material;

[0378] (c) Recover at least a portion of the crystalline material from step (b);

[0379] (d) Optionally, the crystalline material recovered in step (c) is treated to remove at least a portion of the structure-directing agent (Q); and

[0380] (e) Optionally, at least a portion of the boron atoms in the silicate framework are exchanged with aluminum atoms.

[0381] Implementation Scheme 17: The method of Implementation Scheme 16, wherein the synthetic mixture has the following composition expressed in molar ratios:

[0382] molar ratio Typical range Preferred range More preferred range Si / B 10-100 15-75 20-50 Q / Si 0.01-1.0 0.05-1.0 0.1-0.8 F / Si 0-<0.1 0-0.05 0-0.01 OH / Si 0-1.5 0.05-1.0 (if OH is present) 0.1-0.8 (if OH is present) M / Si 0-1.5 0.05-1.0 (if M exists) 0.05-0.8 (if M exists) H2O / Si 1-100 1-75 1-50

[0383] Implementation Scheme 18: A method for preparing RTH framework-type aluminosilicate molecular sieves, comprising:

[0384] (a) Preparing a synthetic mixture comprising water, a source of silica, a source of alumina, a structure-directing agent (Q), optionally a source of hydroxyl ions (OH), and a source of alkali metal and / or alkaline earth metal elements (M).

[0385] The structure-directing agent (Q) comprises the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I:

[0386] and

[0387] The synthetic mixture contains fluoride ions (F) at an F / Si molar ratio of less than 0.1;

[0388] (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 crystalline material;

[0389] (c) Recover at least a portion of the crystalline material from step (b); and

[0390] (d) Optionally, the crystalline material recovered in step (c) is treated to remove at least a portion of the structure-directing agent (Q).

[0391] Implementation Scheme 19: The method of Implementation Scheme 18, wherein the synthetic mixture has the following composition expressed in molar ratios:

[0392] molar ratio Typical range Preferred range More preferred range Si / B 10-100 15-75 20-50 Q / Si 0.01-1.0 0.05-1.0 0.1-0.8 F / Si 0-<0.1 0-0.05 0-0.01 OH / Si 0-2.0 0.1-1.5 (if OH is present) 0.2-1.3 (if OH is present) M / Si 0.1-2.0 0.1-1.5 0.15-1.0 H2O / Si 1-100 10-80 30-70 .

[0393] Implementation Scheme 20: An RTH framework type aluminosilicate molecular sieve that can be obtained by the method described in Implementation Scheme 18 or 19.

[0394] Implementation Scheme 21. An RTH-framework type aluminosilicate molecular sieve having a 1-methyl-6,7-dihydro-5H-cyclopentadiazine-1-onium cation of Formula I within its pore structure:

[0395]

[0396] Implementation Scheme 22: An RTH framework type aluminosilicate molecular sieve having a Si / Al molar ratio of less than 10, preferably having a Si / Al molar ratio of 5 to less than 10.

[0397] Implementation Scheme 23: A method for converting an organic compound into a conversion product, comprising contacting the organic compound with a crystalline material according to any one of Implementation Schemes 4 to 6, 11 to 13 or 20 to 22.

Claims

1. A crystalline material called EMM-64, which, in its calcined form, has an X-ray diffraction pattern comprising at least nine peaks selected from Table 1: Table 1 。 2. The material of claim 1, having an X-ray diffraction pattern comprising all peaks selected from Table 1.

3. The material according to claim 1, having the molecular formula of formula II: (m)X2O3:YO2 (Formula II), Where 0 ≤ m ≤ 0.025, X is Al, and Y is Si.

4. A crystalline material called EMM-64, which, in its original state, has an X-ray diffraction pattern comprising at least seven peaks selected from Table 3: Table 3 。 5. The material of claim 4, having an X-ray diffraction pattern comprising all peaks selected from Table 3.

6. The material of claim 4, having the molecular formula of formula III: (n)Q :(m)X2O3:YO2 (Formula III), Where 0 ≤ n ≤ 0.2, 0 ≤ m ≤ 0.025, and Q is the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I. (Equation I); X is Al, and Y is Si.

7. The crystalline material according to any one of claims 1 to 6, having a framework defined by the connectivity of tetrahedral T atoms in the unit cell as shown in Table 2, wherein the tetrahedral T atoms are connected by bridging atoms: Table 2 a Topologically equivalent atoms have the same "T-type" notation at their positions. b The size and number of the smallest rings at each angle of the T-atom, as described by M. O'Keeffe and ST. Hyde. zeolite As defined in 19,370,1997.

8. A method for preparing EMM-64 crystalline material according to any one of claims 1 to 7, comprising: (a) Preparing a synthetic mixture comprising water, a source of an oxide of a tetravalent element Y, optionally a source of an oxide of a trivalent element X, a structure directing agent Q, a source of fluoride ions F, optionally a source of hydroxide ions OH, and optionally a source of an alkali metal and / or alkaline earth metal element M. The structure-directing agent Q contains the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-onium cation of formula I: (Equation I), The synthetic mixture contains fluoride ions F at an F / Y molar ratio of at least 0.1; and Where X is Al and Y is Si; (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 crystalline material; (c) Recover at least a portion of the crystalline material from step (b); and (d) Optionally, the crystalline material recovered in step (c) is treated to remove at least a portion of the structure-directing agent Q.

9. The method of claim 8, wherein the synthetic mixture has the following composition expressed in molar ratios: 。 10. The method of claim 8, wherein the synthetic mixture has the following composition expressed in molar ratios: 。 11. The method of claim 8, wherein the synthetic mixture has the following composition expressed in molar ratios: 。 12. A method for converting an organic compound into a conversion product, comprising contacting the organic compound with a crystalline material according to any one of claims 1 to 7.

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