EMM-68 aluminosilicate zeolite, its synthesis and applications

Abstract

An aluminosilicate zeolite designated EMM-68, characterized by a unique powder XRD pattern or unique connectivity, a method for its preparation, and uses thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 252,674, filed October 6, 2021, which is incorporated by reference in its entirety. [Technical field]

[0002] The present disclosure relates to aluminosilicate zeolites, methods for their preparation, and uses thereof. [Background technology]

[0003] Molecular sieve materials, both natural and synthetic, can be used as adsorbents and have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AIPOs, and mesoporous materials, are ordered, porous, crystalline materials with well-defined crystal structures as determined by X-ray diffraction (XRD). Certain molecular sieves are ordered and produce specific, identifiable XRD patterns. Within certain molecular sieve materials, there are numerous cavities, which may be interconnected by numerous channels or pores. The size of these cavities and pores is uniform within a particular molecular sieve material. The dimensions of these pores are such that they accept the adsorption of molecules of a certain size while rejecting molecules of larger size. These materials are therefore known as "molecular sieves" and are utilized in various industrial processes, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0004] Molecular sieves applied in catalysis and adsorption include either naturally occurring or synthetic crystalline molecular sieves. Examples of these molecular sieves include large pore zeolites, intermediate pore size zeolites, and small pore zeolites. These zeolites and their isotypes are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, framework type zeolites and other crystalline microporous molecular sieves with established structures are assigned three-letter codes, which are described in Baelocher, L. et al. (2007) "Atlas of Zeolite Framework Types", eds. Elsevier, 6th Edition, which is incorporated herein by reference. These zeolites and their isotypes are also described in the "Database of Zeolite Structures of the IZA Structure Commission". Large pore zeolites generally have a pore size of at least about 7 Å and include LTL, VFI ("extra large" 18R), MAZ, FAU, OFF, *BEA, and MOR framework type zeolites. Examples of large pore zeolites include mazzite, offretite, zeolite L, VPI-5 ("extra large" 18R), zeolite Y, zeolite X, omega, and beta. Intermediate pore size zeolites generally have a pore size of from about 5 Å to at least less than about 7 Å and 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 pore sizes from about 3 Å to less than about 5.0 Å and include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework type zeolites.Examples of small pore zeolites include ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, Zeolite A, chabazite, and ALPO-17.

[0005] The idealized inorganic framework structure of zeolite is a silicate framework, where every tetrahedral atom is connected to the next four tetrahedral atoms by an oxygen atom. As used herein, the term "silicate" refers to a material that includes at least silicon and oxygen atoms that are alternately bonded to each other (i.e., -O-Si-O-Si-), and optionally includes other atoms in an inorganic framework structure, including atoms such as boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc). Atoms other than silicon and oxygen in framework silicates occupy a portion of the lattice sites occupied by silicon atoms in "all-silica" framework silicates. Thus, as used herein, the term "framework silicate" refers to an atomic lattice that includes any of silicates, borosilicates, gallosilicates, ferrisilicates, aluminosilicates, titanosilicates, zincosilicates, vanadosilicates, and the like.

[0006] 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 may determine the type of process to which a given zeolite is applicable. Currently, over 200 unique zeolite framework silicate structures are known and recognized by the Structure Committee of the International Zeolite Association, which defines the various pore shapes and orientations.

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

[0008] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthesis mixture that contains sources of all the elements present in the zeolite, such as alumina, as well as a source of silica. Often, a structure directing agent (SDA) is also present. A structure directing agent is a compound that is believed to facilitate the formation of a molecular sieve and act as a template around which a particular molecular sieve structure can form, thereby facilitating the formation of the desired molecular sieve. A variety of compounds have been used as structure directing agents, including various types of quaternary ammonium cations. Typically, zeolite crystals form around the structure directing agent, and once crystallization is complete, the structure directing agent occupies the pores of the zeolite. Thus, the "as-synthesized" zeolite will contain the structure directing agent within its pores. Therefore, after crystallization, the "as-synthesized" zeolite is typically subjected to a processing step, such as a calcination step, to remove the structure directing agent.

[0009] Although many different zeolites have been discovered, there is a continuing need for new zeolites with desirable properties for gas separation and drying, organic conversion reactions, and other applications. New zeolites can contain novel internal pore structures that can improve selectivity in these processes. Summary of the Invention

[0010] The present disclosure relates to aluminosilicate zeolites, methods for their preparation, and uses thereof.

[0011] In a first embodiment, the present disclosure relates to an aluminosilicate zeolite having, in its as-calcined form (e.g., with at least a portion of the SDA removed), an X-ray diffraction pattern that includes at least five, or six, or preferably all of the peaks at degree 2-theta selected from Table 1:

[0012] [Table 1]

[0013] In a second embodiment, the present disclosure relates to an aluminosilicate zeolite having, in its as-synthesized form (e.g., without the SDA removed), an X-ray diffraction pattern that includes at least 10, or 12, or 13, or preferably all, of the peaks at degree 2 theta selected from Table 2:

[0014] [Table 2]

[0015] In a third embodiment, the present disclosure provides a crystalline crystalline material (whether in the as-synthesized, as-treated (e.g., as-treated with acid or acid and steam), and / or as-calcined form) that is (a) of the C-centered monoclinic space group C2 / m with unit cell dimensions of a=12.4±0.30 Å, b=18.8±0.30 Å, c=9.2±0.30 Å, and β=96.309°, and (b) of 8.0±0.50 Å × 9.4±0.50 Å × 7.7±0. The present invention relates to an aluminosilicate zeolite having a structure with a 10x8x8 channel system with a large cavity size of 50 Å, in which a 10-ring pore along the c-axis has dimensions of 6.1±0.20 Å×3.8±0.20 Å, an 8-ring pore along the b-axis has dimensions of 3.9±0.20 Å×3.3±0.20 Å, and another 8-ring pore in the xy plane has dimensions of 3.9±0.20 Å×3.3±0.20 Å.

[0016] In a fourth embodiment, the present disclosure relates to an aluminosilicate zeolite (whether in the as-synthesized form, the as-treated form (e.g., as-treated with acid or acid and steam), and / or the as-calcined form) having a framework defined by the Table 3 connectivities of tetrahedral (T) atoms in the unit cell, where the tetrahedral (T) atoms are connected by bridging atoms.

[0017] [Table 3]

[0018] In a fifth embodiment, the present disclosure relates to a method for producing an aluminosilicate zeolite, the method comprising the steps of: (a) preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure directing agent (Q), a fluoride source (F), a hydroxide ion source (OH), and optionally an alkali metal cation source or an alkaline earth metal cation source (M), wherein the structure directing agent (Q) is selected from the group consisting of 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation of formula IIIa, 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb, and 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc: [ka] preparing a cation-containing cation-containing compound comprising at least one cation selected from the group consisting of: (b) heating the synthesis mixture under crystallization conditions comprising a temperature of from 100° C. to 200° C. for a time sufficient to form crystals of the aluminosilicate zeolite; (c) recovering at least a portion of the aluminosilicate zeolite from step (b); and (d) optionally treating the aluminosilicate zeolite recovered in step (c) to remove at least a portion of the structure directing agent (Q).

[0019] In a sixth embodiment, the present disclosure relates to a process for converting an organic compound to a conversion product, the process comprising contacting the organic compound with an aluminosilicate zeolite according to the first, second, third, or fourth embodiment, or an aluminosilicate zeolite prepared according to the process of the fifth embodiment.

[0020] These and other features and attributes of the present disclosure, as well as their advantageous applications and / or uses, will become apparent from the following detailed description. Of course, it will be understood that features described in connection with one aspect of the invention may be incorporated in other aspects of the invention. In particular, any two or more features described herein, including in this summary section, may be combined to form a combination of features not specifically described herein. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 shows the powder XRD pattern of the as-synthesized product of Example 2. [Diagram 2] FIG. 2 shows an SEM image of the as-synthesized product of Example 2. [Diagram 3] FIG. 3 shows the powder XRD pattern of the as-calcined product of Example 3. [Figure 4] FIG. 4 shows an SEM image of the as-synthesized product of Example 3. [Figure 5a] Figure 5a shows the structure of EMM-68 material solved by the FOCUS method, where the large spheres represent O atoms and the small spheres represent Si atoms. [Figure 5b] FIG. 5b is similar to FIG. 5a, except that the O atoms have been omitted for clarity. [Figure 6] FIG. 6 shows the configuration of double 5-rings (D5R). [Figure 7] 7a and 7b show an 8-membered ring (8MR) along the

[0010] direction and a 10-membered ring (10MR) along the

[0001] direction. [Figure 8] FIG. 8 shows a large 14-membered ring (14MR) cavity. [Figure 9] FIG. 9 shows the SEM image of the as-synthesized product of Example 4. [Figure 10] FIG. 10 shows the SEM image of the as-synthesized product of Example 5. [Figure 11]FIG. 11 shows the SEM image of the as-synthesized product of Example 6. [Figure 12] FIG. 12 shows the SEM image of the as-synthesized product of Example 7. [Figure 13] FIG. 13 shows the SEM image of the as-synthesized product of Example 10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The present disclosure relates to an aluminosilicate zeolite, a method for its manufacture, and uses thereof. The aluminosilicate zeolite may be designated as EMM-68 zeolite or EMM-68 material.

[0023] The "as-synthesized" (or "as-produced") aluminosilicate zeolites of the present disclosure (i.e., prior to heat treatment or other treatment to remove SDA from the pores) typically contain within their pores SDA, one of the components of the synthesis mixture. Aluminosilicate zeolites of the present disclosure from which some or all of the structure directing agent (SDA) has been removed (e.g., via heat treatment or other treatment to remove SDA from the pores) are at least partially calcined, or "as-calcined" materials.

[0024] In a first embodiment, the present disclosure relates to an aluminosilicate zeolite having, in its as-calcined form (e.g., having at least a portion of the SDA removed), an X-ray diffraction pattern including at least five, or six, or preferably all degree 2-theta peaks selected from Table 1:

[0025] [Table 4]

[0026] In a further embodiment, the aluminosilicate zeolite, in its as-calcined form, may have an X-ray diffraction pattern that includes at least five, or six, or preferably all, of the peaks with degree 2 theta and d-spacing values ​​selected from Table 1A, the d-spacing values ​​having a corresponding deviation determined based on degree 2 theta ±0.20 when converted to the corresponding values ​​of d-spacing using Bragg's law:

[0027] [Table 5]

[0028] The XRD pattern having the XRD peaks described herein is consistent with Cu(K α ) Radiation is used.

[0029] In one or more further embodiments, the aluminosilicate zeolite, in its as-calcined form, may have a micropore volume of 0.10 to 0.40 cc / g, or 0.20 to 0.30 cc / g, such as 0.29 cc / g.

[0030] In one or more further embodiments, the aluminosilicate zeolite, in its as-calcined form, has a calcination rate of 500 to 900 ml. 2 / g, or 600-900m 2 / g, e.g. 700~850m 2 / g, e.g. 774m 2 / g BET surface area.

[0031] In one or more further embodiments, the aluminosilicate zeolite, in its as-calcined form, may optionally be represented by the molecular formula of Formula I: (m)Al 2 O 3 :SiO 2 (Formula I) where 0.0125≦m≦0.1. The oxygen atoms in formula I may be derived from carbon atoms (e.g., CH) that may be derived from the source of the components used to prepare the as-produced aluminosilicate zeolite. 2 In the form of (formula I), the oxygen atom may be replaced by, for example, a nitrogen atom after the SDA has been removed. Formula I may represent the framework of a typical aluminosilicate zeolite as defined in this disclosure in its as-calcined form. Formula I is not meant to be the only representation of said aluminosilicate zeolite. Although said aluminosilicate zeolite in its as-calcined form may contain SDA and / or impurities after appropriate treatment to remove SDA and impurities, these are not taken into account in formula I. Furthermore, formula I does not include protons and charge compensation ions that may be present in said as-calcined aluminosilicate zeolite.

[0032] The variable m represents the Al in formula I. 2 O 3 and SiO 2 For example, when m is 0.05, SiO 2 Al 2 O 3 is 20 and the molar ratio of Si to Al is 10. m may vary from 0.0125 to 0.1, such as at least 0.016, or at least 0.02 to at most 0.083, such as at least 0.025 to at most 0.071. The molar ratio of Si to Al may be from 5 to 40, such as at least 6, or at least 7, and up to 30, or up to 25, or up to 20, such as from 6 to 30 or 25, or from 7 to 20.

[0033] In a second embodiment, the present disclosure relates to an aluminosilicate zeolite, in particular an aluminosilicate zeolite as defined in the first embodiment, which in its as-synthesized form (e.g., in a form in which SDA has not been removed) has an X-ray diffraction pattern that includes at least 10, or 12, or 13, or preferably all, of the peaks at degrees 2 theta selected from Table 2:

[0034] [Table 6]

[0035] In a further embodiment, the aluminosilicate zeolite, in its as-synthesized form, may have an X-ray diffraction pattern that includes at least 10, or 12, or 13, or preferably all, peaks having degrees 2 theta and d-spacing values ​​selected from Table 2A, the d-spacing values ​​having a corresponding deviation determined based on degrees 2 theta ±0.20 when converted to corresponding d-spacing values ​​using Bragg's law.

[0036] [Table 7]

[0037] The XRD pattern having the XRD peaks described herein is consistent with Cu(K α ) Radiation is used.

[0038] In one or more further embodiments, the aluminosilicate zeolite, in its as-synthesized form, may optionally be represented by the molecular formula of Formula II: (n)Q:(m)Al 2 O 3 :SiO 2 (Formula II) wherein 0≦n≦0.7, 0.0125≦m≦0.1, and Q comprises at least one cation selected from the group consisting of the 1,2,3-trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium cation of formula IIIa, the 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb, and the 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc: [ka]

[0039] Formula II may represent the framework of a typical aluminosilicate zeolite as defined in this disclosure in its as-synthesized form, i.e., including the structure directing agent (Q). Formula II is not meant to be the only representation of such materials. The aluminosilicate zeolite, in its as-synthesized form, may include impurities not accounted for in Formula II. Furthermore, Formula II does not include protons and charge compensating ions that may be present in the as-synthesized aluminosilicate zeolite.

[0040] The variable m is the Al in formula II. 2 O 3 SiO 2 The values ​​of the variable m in Formula II are the same as those described herein for Formula I.

[0041] The variable n represents the SiO 2 For example, when n is 0.1, SiO 2 The molar ratio of Q to SiO is 0.1. 2 The molar ratio of Q to may vary from 0 to 0.7, for example, from 0.1, or 0.2, or 0.3 to 0.7.

[0042] In a third embodiment, the present disclosure relates to an aluminosilicate zeolite (whether in the as-synthesized, as-treated (e.g., with acid or acid and steam) and / or as-calcined form) having (a) a C-centered monoclinic space group C2 / m with unit cell dimensions of a=12.4±0.30 Å, b=18.8±0.30 Å, c=9.2±0.30 Å, and β=96.2°, and (b) a structure having a 10×8×8 channel system with large cavity sizes of 8.0±0.50 Å×9.4±0.50 Å×7.7±0.50 Å. The 10-ring pore along the c-axis has dimensions of 6.1±0.20 Å × 3.8±0.20 Å, the 8-ring pore along the b-axis has dimensions of 3.9±0.20 Å × 3.3±0.20 Å, and another 8-ring pore in the xy-plane has dimensions of 3.9±0.20 Å × 3.3±0.20 Å.

[0043] In a fourth embodiment, the present disclosure relates to an aluminosilicate zeolite, in particular an aluminosilicate zeolite as defined in the first, second and / or third embodiment. The aluminosilicate zeolite (whether in the as-synthesized, as-treated (e.g., treated with acid or acid and steam) and / or as-calcined form) has a framework defined by the connectivity in Table 3 of the tetrahedral (T) atoms in the unit cell. The tetrahedral (T) atoms are connected by bridging atoms.

[0044] [Table 8]

[0045] The degree of connectivity can be determined, for example, using the public domain software TOTOPOL by MMJ Treacy et al., available in the “Database of Zeolite Structures of the IZA Structure Commission” (see, for example, MMJ Treacy et al. (2004), Microporous and Mesoporous Materials, Vol. 74, pp. 121-132). The tetrahedral atoms may comprise one or more elements selected from B, Al, Fe, Ga, Si, Ge, Sn, Ti, and Zr, or mixtures thereof. For example, the tetrahedral atoms may be selected from B, Al, or Si, or mixtures thereof. For example, the tetrahedral atoms may comprise or be Si or Al. The bridging atoms may be selected from O, N, and C, or mixtures thereof. The bridging atoms may comprise or be 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). The bridging atom C may be incorporated from various components used to prepare the zeolite, such as the silica source. The bridging atom N may be incorporated into the zeolite after removal of the SDA.

[0046] The aluminosilicate zeolite defined in the first, second, third and / or fourth embodiment may have a Si / Al molar ratio of 5-40, such as 6-30, for example 7-20.

[0047] In a fifth embodiment, the present disclosure relates to a method for producing an aluminosilicate zeolite, in particular an aluminosilicate zeolite as defined in the first, second, third and / or fourth embodiment, comprising the following steps: (a) preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure directing agent (Q), a fluoride ion source (F), a hydroxide ion source (OH), and, optionally, an alkali metal or alkaline earth metal cation source (M); (b) heating the synthesis mixture under crystallization conditions, including a temperature between 100° C. and 200° C., for a time sufficient to form crystals of the aluminosilicate zeolite; (c) recovering at least a portion of the aluminosilicate zeolite from step (b); and (d) optionally treating the aluminosilicate zeolite recovered in step (c) to remove at least a portion of the structure directing agent (Q). Including, The structure directing agent (Q) comprises at least one cation selected from the group consisting of the 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation of formula IIIa, the 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb, and the 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc. [ka]

[0048] The structure directing agent (Q) may be present in any suitable form, for example as a halide such as an iodide or bromide, or as a hydroxide, for example in the form of its hydroxide. The structure directing agent (Q) may be present in the synthesis mixture in a Q / Si molar ratio of 0.05 to 1.0, for example at least 0.1, or at least 0.15, or at least 0.2, up to 0.8, or up to 0.7, or up to 0.6, for example 0.15 to 0.6, for example 0.5.

[0049] The synthesis mixture includes at least one silica source. Suitable silica sources (e.g., silicon oxide sources) include silicates, e.g., tetraalkyl orthosilicates such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), fumed silicas such as Aerosil® (available from Evonik), Cabosperse® (available from Cabot) and Cabosil® (available from DMS), precipitated silicas such as Ultrasil® and Sipernat® 340 (available from Evonik), alkali metal silicates such as potassium silicate and sodium silicate, aqueous colloidal suspensions of silica, e.g., EI du Pont de Gelato silicates ... These include those sold under the trade name Ludox® by Nemours or Aerodisp® by Evonik; preferably, silicates, fumed silica, precipitated silica, alkali metal silicates, colloidal silica, and in particular silicates, such as tetraalkyl orthosilicates, for example tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS).

[0050] The synthesis mixture includes at least one alumina source. Suitable sources of alumina (e.g., aluminum oxide sources) include aluminum salts, particularly water-soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, alkali metal aluminates such as sodium aluminate and potassium aluminate, and aluminum alkoxides such as aluminum isopropoxide, and hydrated aluminum oxides such as boehmite, gibbsite and pseudoboehmite, and mixtures thereof. Other aluminum sources include, but are not limited to, other water-soluble aluminum salts, aluminum alkoxides such as sodium aluminate, aluminum isopropoxide, or aluminum metal, such as aluminum in the form of chips. Particularly suitable alumina sources are water-soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, aluminum alkoxides such as aluminum isopropoxide, and alkali metal aluminates such as sodium aluminate and potassium aluminate.

[0051] Alternatively, or in addition to the aforementioned sources of Si and Al, sources containing both the elements Si and Al can be used. Examples of suitable sources containing both the elements Si and Al include amorphous silica-alumina gel or dry silica-alumina powder, silica-alumina, clays such as kaolin, metakaolin, and zeolites, particularly aluminosilicates such as synthetic faujasite and ultrastable faujasite, e.g., Ultrastable Y (USY), β, or other large to medium pore zeolites.

[0052] The synthesis mixture may have a Si / Al molar ratio of 1 to less than 50, such as 5-40 or 7-25, for example 5-20.

[0053] The synthesis mixture also contains at least one fluoride ion source (F). The fluoride ion source (F) may be any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture. Non-limiting examples of fluoride ion sources (F) include hydrogen fluoride (HF); salts containing one or several fluoride ions, such as metal fluorides, preferably where the metal is sodium, potassium, calcium, magnesium, strontium or barium; ammonium fluoride (NH 4 F); and ammonium difluoride (NH 4 HF 2 Particularly useful sources of fluoride ions include HF, NH 4 F and NH 4 HF 2 and in particular HF. The fluoride ions (F) may be present in an F / Si molar ratio of 0.05 to 1.0, such as 0.2 to 0.8, or 0.3 to 0.7, such as 0.5.

[0054] The synthesis mixture may further optionally contain at least one halide ion source (W) different from fluoride ion, which may be selected from the group consisting of chloride, bromide or iodide. The halide ion source (W) may be any compound capable of releasing halide ions in the molecular sieve synthesis mixture. For example, the halide ion may be present as a counterion of the structure directing agent (Q). Non-limiting examples of sources of halide ions include: hydrogen chloride, ammonium chloride, hydrogen bromide, ammonium bromide, hydrogen iodide, and ammonium iodide; salts containing one or several halide ions, such as metal halides, preferably metal halides, where the metal is sodium, potassium, calcium, magnesium, strontium, or barium; ammonium halides; or tetraalkylammonium halides, such as tetramethylammonium halide or tetraethylammonium halide. The halide ions (W) may be present in a W / Si molar ratio of 0 to 0.2, such as 0 to 0.1, such as less than 0.1 or 0.

[0055] The synthesis mixture includes at least one hydroxide ion (OH) source. For example, hydroxide ions may be present as a counterion of the structure directing agent (Q) or by the use of aluminum hydroxide as an Al source. Suitable sources of hydroxide ions may also be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more often, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most often, sodium hydroxide and / or potassium hydroxide. The synthesis mixture may include a hydroxide ion source with an OH / Si molar ratio of 0.1 to 1.5, for example 0.15 to 1.02, or 0.3 to 0.78, for example 0.5.

[0056] The synthesis mixture may optionally include one or more sources of alkali or alkaline earth metal cations (M). When present, M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, calcium, magnesium and mixtures thereof, and may preferably be sodium and / or potassium, more preferably sodium. When present, the sodium source may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or a sodium salt such as NaCl, NaBr, or sodium nitrate. When present, the potassium source may be potassium hydroxide, potassium aluminate, potassium silicate, a potassium salt such as KCl or KBr, or potassium nitrate. When present, the lithium source may be lithium hydroxide, or a lithium salt such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. When present, the rubidium source may be rubidium hydroxide, or a rubidium salt such as RbCl, RbBr, RbI, or rubidium nitrate. When present, the calcium source may be, for example, calcium hydroxide. When present, the magnesium source may be, for example, magnesium hydroxide. The alkali or alkaline earth metal cations M may also be present in one or more sources of alumina, such as sodium or potassium aluminate, and / or one or more sources of silica, such as sodium and / or potassium silicate. The synthesis mixture may comprise a source of alkali or alkaline earth metal cations (M) in an M / Si molar ratio of 0 to 0.5, such as 0 to 0.1, or 0 to 0.05, such as 0 or 0.05. Alternatively, the synthesis mixture may be free of alkali or alkaline earth metal cations (M).

[0057] The synthesis may be carried out with or without the addition of nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds may be of the same or different structure as the aluminosilicate zeolite of the present disclosure, or EMM-68 material from a previous synthesis. Suitably, the seeds may be present in an amount of about 0.01 ppm to about 10,000 ppm by weight based on the synthesis mixture, for example, about 100 ppm to about 5,000 ppm by weight based on the weight of the synthesis mixture.

[0058] Typically, the synthesis mixture contains 1-100, e.g., 1-75, or 2-50, e.g., 1, 2, 3, or 4, up to 50, or 25, or 10, e.g., 4 H 2 Depending on the nature of the components in the base mixture, the amount of solvent of the base mixture (e.g., water from the hydroxide solution, and optionally methanol and ethanol from hydrolysis of the silica source) may be removed from the base mixture to achieve the desired solvent to Si molar ratio for the synthesis mixture. Suitable methods for reducing the solvent content may include evaporation under a static or flowing atmosphere such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. If too much water is removed in the solvent removal process, water may be added to the resulting mixture to obtain the desired H 2 In some cases, the preparation may achieve a molar ratio of H 2 With an O / Si molar ratio, water removal is not necessary.

[0059] CH 2 Carbon in the form of may be present in various sources of components used to prepare the aluminosilicate zeolites of the present disclosure, such as silica or alumina sources, and may be incorporated into the framework of the aluminosilicate zeolite as a bridging atom. Nitrogen atoms may be incorporated into the framework of the aluminosilicate zeolite as a bridging atom after SDA is removed.

[0060] In one or more embodiments, the synthesis mixture after solvent adjustment (e.g., a desired ratio of water to silica is achieved) may be mixed by a mechanical process such as stirring or high shear blending, for example, using a dual asymmetric centrifugal mixer (e.g., FlackTek speedmixer) with a mixing speed of 1000 rpm to 3000 rpm (e.g., 2000 rpm) to ensure suitable homogenization of the base mixture.

[0061] The synthesis mixture is then subjected to suitable crystallization conditions for the formation of the aluminosilicate zeolite. The crystallization of the aluminosilicate zeolite may be carried out under static or stirred conditions in a suitable reaction vessel, such as a Teflon® lined or stainless steel autoclave, placed in a convection oven maintained at a suitable temperature.

[0062] The crystallization in step (b) of the method is typically carried out at a temperature between 100°C and 200°C, for example between 120°C and 170°C, for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time may be shortened. For example, the crystallization conditions in step (b) of the method may include heating for a period of 1 day to 100 days, for example between 1 day and 50 days, for example between 1 day and 30 days, for example at least 1 day or at least 5 days, up to 20 days or 15 days. The crystallization time can be established by methods known in the art, such as sampling the synthesis mixture at various times and determining the yield and X-ray crystallinity of the precipitated solid. Unless otherwise indicated herein, the temperature measured is the temperature of the surrounding environment of the material being heated, for example the temperature of the atmosphere in which the material is heated.

[0063] Typically, the aluminosilicate zeolite is formed in solution and can be recovered by standard means such as centrifugation or filtration, and the separated aluminosilicate zeolite can also be washed, recovered by centrifugation or filtration, and dried.

[0064] The aluminosilicate zeolites of the present disclosure, when employed as adsorbents or catalysts in organic compound conversion processes, may be at least partially dehydrated (e.g., dried). This can be done by heating in an atmosphere of air, nitrogen, or the like at atmospheric, subatmospheric, or superatmospheric pressures at temperatures ranging from 80° C. to 500° C., e.g., 90° C. to 370° C., for 30 minutes to 48 hours. Dehydration can also be achieved at room temperature by simply placing the molecular sieve in a vacuum, but longer times are required to obtain sufficient dehydration.

[0065] As a result of the crystallization process, the recovered product contains within its pores at least a portion of the structure directing agent used in the synthesis. The as-synthesized aluminosilicate zeolite recovered from step (c) may therefore be subjected to heat or other treatments to remove some or all of the SDA that was incorporated within its pores during synthesis. Heat treatment (e.g., calcination) of the as-synthesized aluminosilicate zeolite typically involves subjecting 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 subatmospheric pressures can be employed for the heat treatment, atmospheric pressure is preferred for convenience. Heat treatment can be carried out at temperatures up to 925°C, for example, between 300°C and 700°C or between 400°C and 600°C. The temperature measured is that of the ambient environment of the sample. Heat treatment (e.g., calcination) can be carried out in a box furnace in dry air exposed to a drying tube containing a desiccant that removes moisture from the air. Typically, the heating is performed for at least one minute, typically for one or up to several days. Heating may be performed initially under a nitrogen atmosphere, then the atmosphere may be switched to air and / or ozone.

[0066] The aluminosilicate zeolite can also be subjected to an ion exchange treatment using aqueous ammonium salts, such as ammonium nitrate, ammonium chloride, and ammonium acetate, to remove the remaining alkali metal and / or alkaline earth metal cations and replace them with protons, thereby producing the acid form of the molecular sieve. The original cations of the as-synthesized material, such as alkali metal cations, can be replaced by ion exchange with other cations. Preferred replacement cations can include hydrogen ions, hydrogen precursors, such as ammonium ions, and mixtures thereof. The ion exchange step can be performed after the as-produced molecular sieve is dried. The ion exchange step can be performed before or after the calcination step.

[0067] The aluminosilicate zeolites may also be subjected to other treatments, such as steaming and / or washing with solvents, which are known to those skilled in the art and are carried out to modify the properties of the molecular sieve as desired.

[0068] The aluminosilicate zeolite of the present disclosure from which some or all of the SDA has been removed may be used as an adsorbent or as a catalyst or support for a catalyst in a wide variety of hydrocarbon conversions, such as the conversion of organic compounds to conversion products. Thus, in a sixth embodiment, the present disclosure relates to the use of the aluminosilicate zeolite described herein as an adsorbent or as a catalyst or support for a catalyst in hydrocarbon conversion. The present disclosure also relates to a process for converting organic compounds to conversion products, comprising contacting the aluminosilicate zeolite described herein with the organic compound.

[0069] The aluminosilicate zeolite (from which some or all of the SDA has been removed) of the present disclosure may be used as an adsorbent, for example, to separate at least one component from a mixture of components in a gas or liquid phase that has differential sorption characteristics for the material. Thus, at least one component can be partially or substantially completely separated from a mixture of components that has differential sorption characteristics for the aluminosilicate zeolite by contacting the mixture with the aluminosilicate zeolite to selectively adsorb the at least one component. For example, in a process for selectively separating one or more desired components of a feedstock from the remaining components of the feedstock, the feedstock may be contacted with a sorbent comprising an aluminosilicate zeolite of the present disclosure under effective sorption conditions. This may result in the formation of a sorption product and an effluent product. The one or more desired components are recovered from either the sorption product or the effluent product.

[0070] The aluminosilicate zeolites of the present disclosure (with some or all of the SDA removed) may also be used as catalysts to catalyze a wide variety of organic compound conversion processes. Examples of chemical conversion processes that can be effectively catalyzed by the aluminosilicate zeolites described herein, alone or in combination with one or more other catalytically active materials, including other crystalline catalysts, include those that require a catalyst with acid activity. Examples of organic conversion processes that can be catalyzed by the aluminosilicate zeolites described herein include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, transalkylation, dealkylation, hydrodesilylation, disproportionation, oligomerization, dehydration cyclization, methanol to olefins, deNOx applications, and combinations thereof. The conversion of the hydrocarbon feed can be carried out in any convenient manner, such as, for example, in a fluidized bed, moving bed, or fixed bed reactor, depending on the type of process desired.

[0071] The aluminosilicate zeolites of the present disclosure may be formulated into product compositions in combination with other materials, such as binders and / or matrix materials that provide additional hardness to the final product. These other materials may be inert or catalytically active materials.

[0072] For example, it may be desirable to incorporate the aluminosilicate zeolites of the present disclosure with another material that is resistant to the temperatures and other conditions employed during use. Such materials include synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, metal oxides such as silica and / or alumina, and mixtures thereof. The metal oxides may be naturally occurring or in the form of gel-like precipitates or gels, including mixtures of silica and metal oxides. The use of resistant materials in conjunction with, i.e. in combination with, the aluminosilicate zeolites of the present disclosure, or present during the synthesis of as-produced aluminosilicate zeolites in which the crystals are active, tends to alter the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inert resistant materials suitably function as diluents to control the amount of conversion in a given process, so that products can be obtained in an economical and orderly manner without employing other means to control the reaction rate. These materials may be incorporated into naturally occurring clays, such as bentonite and kaolin, to improve the crush strength of the product under commercial operating conditions. The inert resistant materials, i.e. clays, oxides, etc., act as binders for the catalyst. In commercial use, it is desirable to prevent the catalyst from breaking down into powdery materials, so a catalyst with good crush strength can be beneficial.

[0073] Naturally occurring clays that may be used include the montmorillonite and kaolin families. The family includes subbentonites and kaolins, commonly known as Dixie, McNamee, Georgia, and Florida clays, whose major mineral components are halloysite, kaolinite, dickite, nacrite, or anorthite. Such clays may be used in their raw state as mined, or after calcination, acid treatment, or chemical modification. Binders useful for compositing with the aluminosilicate zeolites of the present disclosure also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallium oxide, zinc oxide, and mixtures thereof.

[0074] In addition to the aforementioned materials, the aluminosilicate zeolites of the present disclosure may be composited with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0075] These binder materials are resistant to the temperatures and other conditions, such as mechanical wear, encountered in various hydrocarbon separation processes. Thus, the aluminosilicate zeolites of the present disclosure may be used in the form of extrudates with a binder. Typically, they are bound by forming tablets, spheres, or extrudates. Usually, extrudates are formed by extruding the molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudates. Optionally, further processing, such as steaming and / or ion exchange, may be carried out. Optionally, the aluminosilicate zeolites may be bound by a binder for at least 100 m. 2 / g, e.g. at least 200m 2 / g, if necessary, at least 300m 2 The molecular sieve may be combined with a binder having a surface area of ​​about 100 nm / g.

[0076] The relative proportions of aluminosilicate zeolite and inorganic oxide matrix may vary widely, with the aluminosilicate zeolite content ranging from about 1 to about 100 weight percent, more usually from about 2 to about 95 weight percent, and optionally from about 20 to about 90 weight percent of the composite, especially when the composite is prepared in the form of an extrudate.

[0077] Also, when performing a hydrogenation-dehydrogenation function, the aluminosilicate zeolite of the present disclosure can be used in intimate combination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a precious metal such as platinum or palladium. Such hydrogenation components can be incorporated into the composition by one or more of the following processes: co-crystallization; exchange into the composition to the extent that a Group IIIA element, such as aluminum, is present in the structure; or intimate physical intermixing therewith. Such components can also be impregnated into or on the aluminosilicate zeolite, for example, by treating the molecular sieve with a hydrogenation metal-containing ion. For example, in the case of platinum, platinum compounds suitable for this purpose include various compounds including chloroplatinic acid, chloroplatinic acid, and platinum amine complexes. Combinations of metals and methods of incorporation thereof can also be used.

[0078] Those skilled in the art will appreciate that the aluminosilicate zeolites of the present disclosure may contain impurities such as amorphous materials, unit cells with different topologies (e.g., quartz or molecular sieves of different framework types that may or may not affect the performance of the resulting catalyst), and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). Representative examples of molecular sieves or zeolites of different framework types that may coexist with the aluminosilicate zeolites of the present disclosure include, for example, HEU framework type molecular sieves and / or layer phases of PREFER zeolites. phase), as well as layer phase zeolites of potentially unknown framework type. The aluminosilicate zeolites of the present disclosure are preferably substantially free of impurities. As used herein, the term "substantially free of impurities" (or alternatively "substantially pure") means that the aluminosilicate zeolites contain a small percentage (less than 50 wt%) of these impurities, 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 less than 0.1 wt%). The weight percent (wt%) values ​​are based on the combined weight of the impurities and the pure aluminosilicate zeolites. The amount of impurities may be suitably determined by powder XRD, rotational electron diffraction, and / or SEM / TEM (e.g., different crystal morphologies).

[0079] The aluminosilicate zeolites described herein are substantially crystalline. As used herein, the term "crystalline" refers to a crystalline solid form of a material. It includes, but is not limited to, single or multi-component crystalline forms, including, for example, solvates, hydrates, and co-crystals. Crystallinity can mean having a regular repeat and / or regular arrangement of molecules and having a distinguishable crystal lattice. For example, aluminosilicate zeolites can have different moisture or solvent contents. The different crystal lattices can be identified by solid state characterization methods such as XRD (e.g., powder XRD). Other characterization methods known to those of ordinary skill in the relevant art can further help identify the crystalline form as well as help determine stability and solvent / water content. As used herein, the term "substantially crystalline" means that the majority (greater than 50 wt%) of the weight of a sample of the described material is crystalline, with the remainder of the sample being in an amorphous form. In one or more embodiments, a 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).

[0080] The aspects of the present disclosure will be described in more detail by specific examples.The following examples are provided for illustrative purposes and are not intended to limit the present disclosure in any manner.Those skilled in the art in the relevant technical field will easily recognize that various parameters can be changed or modified to obtain essentially the same results. EXAMPLES

[0081] The present invention is further illustrated below, without limiting its scope.

[0082] In these examples, X-ray diffraction (XRD) patterns of the as-synthesized and as-calcined materials were recorded in continuous mode on an X-ray powder diffractometer (Bruker DaVinci D8 Discovery instrument) using CuKα radiation in Bragg-Bentano geometry with a Vantec 500 detector in the 2θ range of 4 to 60 degrees. Interplanar spacings, d-spacings, are calculated in angstroms, and relative line intensities I / I o is the ratio of the peak intensity to the intensity of the most intense line above background. Intensities are uncorrected for Lorentz and polarization effects. The positions of the diffraction peaks at 2θ, and the relative peak area intensity of the lines, I / I(o), were determined using the MDI Jade peak search algorithm, where Io is the intensity of the most intense line above background. It should be understood that the diffraction data described as a single line may be composed of multiple overlapping lines that may appear as resolved or partially resolved lines under certain conditions, such as differences in crystallographic changes. Typically, crystallographic changes may include slight changes in unit cell parameters and / or changes in crystal symmetry, even without changes in framework connectivity. These minor effects, including changes in relative intensity, may also result from differences in cation content, framework composition, nature and degree of pore filling, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0083] Scanning electron microscope (SEM) images of the as-synthesized material were obtained on a Hitachi 4800 scanning electron microscope. The SEM images served to assess the purity of the product. The presence of distinctly different crystalline morphologies in the SEM images may indicate the presence of impurities in the form of other crystalline materials. Such proximate analysis may be particularly useful in identifying the presence of relatively small amounts of crystalline impurity formation that may not be discernible in the XRD pattern of the product.

[0084] The fired samples were subjected to the following measurements.

[0085] The overall BET surface area of ​​the material (S BET) was measured by the BET method using nitrogen adsorption-desorption at liquid nitrogen temperatures as described by S. Brunauer et al. (1938), J. Am. Chem. Soc., Vol. 60, p. 309, which is incorporated herein by reference.

[0086] The micropore volume of the material (V micro ) can be determined using methods known in the relevant art. For example, the micropore volume of a material can be measured by nitrogen physisorption and the data analyzed by the t-plot method as described in Lippens, BC et al. (1965) "Studies on pore system in catalysts: V. The t method", J. Catal., Vol. 4, p. 319, which describes the micropore volume method and is incorporated herein by reference.

[0087] Alpha value is a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 3,354,078, and in Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each of which is incorporated herein by reference. The experimental conditions for the tests used herein include a constant temperature of 538° C. and variable flow rates, as described in detail in Journal of Catalysis, Vol. 61, p. 395.

[0088] The molar ratios and conditions used in the synthesis of Examples 1-11, and the resulting products, are detailed below and summarized in Table 4.

[0089] Example 1a: Synthesis of 1,2,3-trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium cation of formula IIIa 2-Methyl-4,5,6,7-tetrahydro-1H-benzimidazole: 40 g of 2-methylbenzimidazole were dissolved in 320 ml of glacial acid. 15 g of palladium (10 wt% on carbon) were added and the reaction mixture was treated with hydrogen at a temperature of 120° C. and under a pressure of 80 bar for 24 hours. The solution was filtered over Celite and washed with glacial acid. The solvent was evaporated under vacuum and then aqueous sodium hydroxide solution was added to bring the pH of the solution to 9-10. The precipitate was filtered, washed with water, then dissolved in chloroform and extracted with saturated aqueous sodium chloride solution. The organic phase was dried over sodium sulfate, filtered and concentrated under vacuum.

[0090] 1,2,3-Trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium iodide: 13.6 g of 2-methyl-4,5,6,7-tetrahydro-1H-benzimidazole, 70 g of iodomethane, and 27 g of potassium carbonate were dissolved in 150 ml of acetonitrile (CH) in a 250 mL round-bottom flask equipped with a magnetic stir bar. 3 CN). The suspension was refluxed for 18 hours and then cooled to room temperature. The solution was filtered through a Büchner funnel and the filtrate was concentrated on a rotovap. Dichloromethane was added to the concentrate to remove residual potassium salts. The filtrate in dichloromethane was concentrated on a rotovap and dried under vacuum to give 1,2,3-trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium iodide.

[0091] 1,2,3-Trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium hydroxide:iodide salt was ion-exchanged to the hydroxide form with ion-exchange resin Amberlite® IRN78 OH hydroxide form (iodide:resin:water ratio 1:3.5:5) at room temperature overnight.

[0092] Example 1b: Synthesis of 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb 45g of K 2 CO 3was added to a solution of 18 g of 4,5,6-trimethylpyrazole in acetonitrile (300 mL). After stirring for 30 minutes at ambient temperature, 70 g of 1,4-dibromobutane was added. The reaction mixture was stirred at ambient temperature for 4 hours and then the temperature was raised to 90° C. for 36 hours. The mixture was cooled to ambient temperature and the solvent was evaporated under reduced pressure. The residue was taken up in dichloromethane and the resulting suspension was filtered. The solvent was removed in vacuum to give a solid product.

[0093] The bromide salt was then ion-exchanged to the hydroxide form with Amberlite® IRN78 OH hydroxide form (bromide:resin:water ratio 1:3.5:5) ion exchange resin at room temperature overnight.

[0094] Example 1c: Synthesis of 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc 22g of K 2 CO 3 was added to a solution of 9 g of 4,5,6-trimethylpyrazole in acetonitrile (160 mL). After stirring for 30 minutes at ambient temperature, 49 g of 1,3-dibromopropane was added. The reaction mixture was stirred at ambient temperature for 4 hours, after which the temperature was raised to 90° C. for 36 hours. The mixture was cooled to ambient temperature and the solvent was evaporated under reduced pressure. The residue was taken up in dichloromethane and the resulting suspension was filtered. The solvent was removed in vacuum to give a solid product.

[0095] The bromide salt was then ion-exchanged to the hydroxide form with Amberlite® IRN78 OH hydroxide form (bromide:resin:water ratio 1:3.5:5) ion exchange resin at room temperature overnight.

[0096] Example 2: Synthesis of EMM-68 using the cation of formula IIIa with aluminum hydroxide, with a molar ratio of Si / Al of 10 2.55 g of tetraethyl orthosilicate (TEOS, >99 wt%) and 0.116 g of Al(OH) 3(Sigma, 54 wt%) was hydrolyzed in 5.31 g of 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium hydroxide (21 wt% solution) at room temperature for approximately 2-3 hours. The mixture was then heated at approximately 50 °C to remove ethanol and water. 0.26 g of HF (48 wt% solution) was added to the mixture to produce a synthesis mixture with the following composition in molar ratios: 4H 2 O:1SiO 2 :0.05Al 2 O 3 :0.5QOH:0.5HF

[0097] The resulting thick paste was hand homogenized in Teflon and transferred to a 23 mL Teflon-lined stainless steel autoclave (Parr). The autoclave was heated in a tumbling oven (approximately 40 rpm) at 150° C. for 14 days. After 14 days, the reactor was discharged and the product was collected by centrifugation and washed three times with distilled water (200 mL). The product was dried at 90° C. in a vented drying oven. The as-synthesized material was then calcined in a box furnace in air at a heating rate of 3° C. / min to 580° C. The temperature of 580° C. was held for 8 hours, after which the box furnace was cooled.

[0098] XRD analysis of the as-synthesized material showed that the material had a unique powder XRD pattern that did not match any known zeolites and was designated as the pure as-synthesized EMM-68 product. Figure 1 shows the powder XRD of the as-synthesized product. Figure 2 shows an SEM image of the as-synthesized product.

[0099] Example 3: Synthesis of EMM-68 with a molar ratio of Si / Al of 12.5 and a cation of formula IIIa using aluminum hydroxide This example was carried out under the same conditions and with the same molar ratios as in Example 2, except that the Si / Al molar ratio of the synthesis mixture was 12.5. After heating at 150° C. for 14 days, a pure EMM-68 product was obtained, as identified by its XRD pattern.

[0100] Tables 5 and 6 below show the list of peaks and intensities for the as-synthesized and as-calcined EMM-68 products of Example 2, respectively. Figure 3 shows the powder XRD of the as-calcined product. Figure 4 is an SEM image of the as-synthesized product.

[0101] The structure of EMM-68 was determined from powder XRD data using the FOCUS Fourier recycle technique. EMM-68 exhibits a C-centered monoclinic space group C2 / m with unit cell dimensions of a=12.4±0.30 Å, b=18.8±0.30 Å, c=9.2±0.30 Å, and β=96.2°. The EMM-68 material has a 15T / 1000 Å 3 It has a framework density of 10x8x8 with 32 T atoms in one unit cell. The EMM-68 material has a 10x8x8 channel system with a large cavity size of 8.0±0.50Å×9.4±0.50Å×7.7±0.50Å. The 10-ring pore along the c-axis has dimensions of 6.1±0.20Å×3.8±0.20Å, the 8-ring pore along the b-axis has dimensions of 3.9±0.20Å×3.3±0.20Å, and another 8-ring pore in the xy plane has dimensions of 3.9±0.20Å×3.3±0.20Å. Figures 5a and 5b show the structure of the EMM-68 material analyzed by the FOCUS method. In Figure 5a, the oxygen atoms are large spheres and the Si atoms are small spheres. In Figure 5b, the oxygen atoms have been omitted for clarity. EMM-68 is constructed by placing double 5-rings (D5Rs) as the only complex building blocks, as shown in Figure 6. Figure 7a shows an 8-membered ring (8MR) along the

[0010] direction. Figure 7b shows a 10-membered ring (10MR) along the

[0001] direction. Figure 8 shows a large 14-membered ring (14MR) cavity.

[0102] Thermogravimetric analysis (TGA) was performed on the as-synthesized EMM-68 product by heating from room temperature to 800 °C in air. There is a cumulative mass loss of 10 wt% up to 230 °C, which can be attributed to water, and a mass loss of 23 wt% from 230 °C to 800 °C, which can be attributed to the removal of approximately four molecules of structure directing agent (Q) per unit cell.

[0103] The as-synthesized EMM-68 material was calcined according to the procedure specified in Example 2.

[0104] The BET surface area (S BET ) is 774m 2 / g, and its micropore volume (V micro ) was 0.29 cc / g and its alpha value was 66. The uptake of n-hexane, 2,2-dimethylbutane (2,2-DMB), 2,3-dimethylbutane (2,3-DMB), and mesitylene was determined on the ion-exchanged and calcined material. The material was placed under a nitrogen stream and then a hydrocarbon was introduced through a sparger to saturate the nitrogen stream and the uptake of the hydrocarbon was determined. Each hydrocarbon was adsorbed at a different temperature. n-Hexane was adsorbed at 90°C, 2,2-DMB was adsorbed at 120°C, 2,3-DMB was adsorbed at 120°C, and mesitylene was adsorbed at 100°C. The uptake of n-hexane was 103.4 mg / g, that of 2,2-DMB was 91.9 mg / g, that of 2,3-DMB was 61.8 mg / g, and that of mesitylene was 26.1 mg / g.

[0105] Examples 4-8: Synthesis of EMM-68 using aluminum isopropoxide with various Si / Al molar ratios and the cation of formula IIIa These examples were carried out under the same conditions as Examples 2-3, except that aluminum isopropoxide (98 wt%, Sigma) was used as the Al source, varying the Si / Al molar ratio to 10, 12.5, 15, 20 and 50, respectively. After heating at 150 °C for 14 days, pure EMM-68 products were obtained for Examples 4-7, as identified by XRD patterns. Example 8 was carried out with a Si / Al ratio of 50, resulting in a layer phase. Figures 9-12 show SEM images of the as-synthesized products of Examples 4, 5, 6 and 7, respectively.

[0106] Example 9: Synthesis of EMM-68 using cation of formula IIIa with USY zeolite at Si / Al molar ratio of 10 This example was carried out under the same conditions as Example 2, except that USY zeolite with a Si / Al molar ratio of 15 (available from Zeolyst as CBV720) was used as the Si source, and USY zeolite with a Si / Al molar ratio of 6 (available from Zeolyst as CBV712) ​​was used as the Al source. After heating at 150° C. for 14 days, a pure EMM-68 product was obtained, as identified by the XRD pattern.

[0107] Example 10: Synthesis of EMM-68 using cation of formula IIIa with USY zeolite at Si / Al molar ratio of 6 This example was carried out under the same conditions as Example 9, except that USY zeolite (available from Zeolyst as CBV712) ​​with a Si / Al molar ratio of 6 was used as the Si and Al sources, and NaOH (4 wt% solution) was added to the gel mixture with a NaOH / Si molar ratio of 0.05. After heating at 150° C. for 14 days, a pure EMM-68 product was obtained, as identified by the XRD pattern. Figure 13 shows the SEM image of the as-synthesized product.

[0108] Example 11: Synthesis of EMM-68 using the cation of formula IIIb This example was carried out under the same conditions as Example 3, except that 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium hydroxide was used as the structure directing agent (Q). After heating at 150° C. for 14 days, an EMM-68 product was obtained containing the HEU phase as a trace impurity, which was identified by its XRD pattern.

[0109] Example 12: Synthesis of EMM-68 using the cation of formula IIIc This example was carried out under the same conditions as Example 3, except that 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium hydroxide was used as the structure directing agent. After heating at 160° C. for 14 days, a pure EMM-68 product was obtained, as identified by its XRD pattern.

[0110] [Table 9]

[0111] [Table 10]

[0112] [Table 11]

[0113] Although the present invention has been described and illustrated with reference to specific embodiments, those skilled in the art will understand that the present invention is suitable for many different changes, modifications and variations not specifically illustrated herein. It will also be apparent to those skilled in the art that when numerical lower limits and numerical upper limits are described herein, ranges from any lower limit to any upper limit are contemplated. In addition, all numerical values ​​in the detailed description of the present specification are modified by the indicated value "about" to take into account experimental error and variation expected by those skilled in the art.

[0114] Where the foregoing description refers to integers or elements having known, obvious or foreseeable equivalents, such equivalents are incorporated herein as if set forth individually. Reference should be made to the claims to determine the true scope of the invention, which should be interpreted to encompass any such equivalents. The reader will also understand that integers or features of the invention described as preferred, advantageous, convenient, etc. are optional and do not limit the scope of the independent claims. It should further be understood that such optional integers or features may be beneficial in some embodiments of the invention, while being undesirable and therefore absent in other embodiments.

[0115] Additionally or alternatively, the present invention relates to:

[0116] Embodiment 1: An aluminosilicate zeolite, in its as-calcined form, having an X-ray diffraction pattern comprising at least five peaks selected from Table 1.

[0117] Embodiment 2: An aluminosilicate zeolite according to embodiment 1, having in its as-calcined form an X-ray diffraction pattern including at least six peaks, preferably all peaks, selected from Table 1.

[0118] Embodiment 3: An aluminosilicate zeolite according to embodiment 1 or 2, having the molecular formula of Formula I: (m)Al 2 O 3 :SiO 2 (Formula I) [In the formula, 0.0125 <m≦0.1である。]

[0119] Embodiment 4: An aluminosilicate zeolite, in as-synthesized form, having an X-ray diffraction pattern comprising at least 10 peaks selected from Table 2.

[0120] Embodiment 5: An aluminosilicate zeolite according to embodiment 4, having an X-ray diffraction pattern that includes at least 12, preferably at least 13, more preferably all of the peaks selected from Table 2 in as-synthesized form.

[0121] Embodiment 6: An aluminosilicate zeolite according to embodiment 4 or 5, having a molecular formula of Formula II: (n)Q:(m)Al 2 O 3 :SiO 2 (Formula II) wherein 0≦n≦0.7, 0.0125≦m≦0.1, and Q comprises at least one cation selected from the group consisting of the 1,2,3-trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium cation of formula IIIa, the 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo"1,2-a]pyridazin-4-ium cation of formula IIIb, and the 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo"1,2-a]pyrazol-4-ium cation of formula IIIc. [ka]

[0122] Embodiment 7: An aluminosilicate zeolite according to any one of embodiments 1 to 6, having a framework defined by the following connectivity in Table 3 for the tetrahedral (T) atoms in the unit cell, wherein the tetrahedral (T) atoms are connected by bridging atoms.

[0123] Embodiment 8: The aluminosilicate zeolite according to any one of the preceding embodiments, having a structure with (a) a C-centered monoclinic space group C2 / m with unit cell dimensions of a=12.4±0.30 Å, b=18.8±0.30 Å, c=9.2±0.30 Å, and β=96.2°, and (b) a 10×8×8 channel system with a large cavity size of 8.0±0.50 Å×9.4±0.50 Å×7.7±0.50 Å, wherein a 10-ring pore along the c-axis has dimensions of 6.1±0.20 Å×3.8±0.20 Å, an 8-ring pore along the b-axis has dimensions of 3.9±0.20 Å×3.3±0.20 Å, and another 8-ring pore in the xy-plane has dimensions of 3.9±0.20 Å×3.3±0.20 Å.

[0124] Embodiment 9: The aluminosilicate zeolite according to any one of embodiments 1 to 8, having a Si / Al molar ratio of 5-40, preferably 6-30, more preferably 7-20.

[0125] Embodiment 10: A method for producing the aluminosilicate zeolite of any one of embodiments 1 to 9, comprising: (a) preparing a synthesis mixture comprising water, a source of silica, a source of alumina, a source of structure directing agent (Q), a source of fluoride (F), a source of hydroxide ions (OH), and optionally a source of alkali metal or alkaline earth metal cations (M); (b) heating the synthesis mixture under crystallization conditions, including a temperature of from 100° C. to 200° C., for a time sufficient to form crystals of the aluminosilicate zeolite; (c) recovering at least a portion of the aluminosilicate zeolite from step (b); and (d) optionally treating the aluminosilicate zeolite recovered in step (c) to remove at least a portion of the structure directing agent (Q). Including, The structure directing agent (Q) comprises at least one cation selected from the group consisting of the 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation of formula IIIa, the 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb, and the 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc. [ka]

[0126] Embodiment 11: The method of embodiment 10, wherein the structure directing agent (Q) is in its hydroxide form.

[0127] Embodiment 12: The method of embodiment 10 or 11, wherein the synthesis mixture has the following composition in molar ratio:

[0128] [Table 12]

[0129] Embodiment 13: A process for converting an organic compound to a conversion product, comprising contacting the organic compound with the aluminosilicate zeolite of any one of embodiments 1 to 9.

Claims

1. An aluminosilicate zeolite having, in its as-calcined form, an X-ray diffraction pattern comprising at least five peaks selected from Table 1. 【Table 1】

2. 2. The aluminosilicate zeolite of claim 1, which in its as-calcined form has an X-ray diffraction pattern comprising at least six peaks, preferably all peaks, selected from Table 1.

3. Formula I: (m)Al ２ Oh ３ :SiO ２ (formula I), having the molecular formula 2. The aluminosilicate zeolite according to claim 1, wherein m is 0.0125<m≦0.

1.

4. An aluminosilicate zeolite having, in its as-synthesized form, an X-ray diffraction pattern comprising at least 10 peaks selected from Table 2. 【Table 2】

5. 5. The aluminosilicate zeolite of claim 4, having, in its as-synthesized form, an X-ray diffraction pattern comprising at least 12 peaks, preferably at least 13 peaks, more preferably all peaks selected from Table 2.

6. Formula II: (n)Q:(m)Al ２ O ３ :SiO ２ (Formula II), having the molecular formula wherein 0≦n≦0.7, 0.0125≦m≦0.1, and Q is a 1,2,3-trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium cation of formula IIIa, a 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb, and a 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc: 【Chemical 1】 5. The aluminosilicate zeolite of claim 4, comprising at least one cation selected from the group consisting of:

7. 7. The aluminosilicate zeolite of any one of claims 1 to 6, having a framework defined by the following connectivity in Table 3 for the tetrahedral (T) atoms in the unit cell, wherein the tetrahedral (T) atoms are connected by bridging atoms. 【Table 3】

8. (a) C-centered monoclinic space group C2 / m with unit cell dimensions of a = 12.4 ± 0.30 Å, b = 18.8 ± 0.30 Å, c = 9.2 ± 0.30 Å, and β = 96.2°; and (b) A 10x8x8 channel system with a large cavity size of 8.0±0.50 Å × 9.4±0.50 Å × 7.7±0.50 Å. and a structure having the formula:

7. The aluminosilicate zeolite of any one of claims 1 to 6, wherein a 10-ring pore along the c-axis has dimensions of 6.1±0.20 Å x 3.8±0.20 Å, an 8-ring pore along the b-axis has dimensions of 3.9±0.20 Å x 3.3±0.20 Å, and another 8-ring pore in the xy plane has dimensions of 3.9±0.20 Å x 3.3±0.20 Å.

9. 7. An aluminosilicate zeolite according to any one of claims 1 to 6, having a Si / Al molar ratio of 5 to 40, preferably 6 to 30, more preferably 7 to 20.

10. A method for producing the aluminosilicate zeolite according to any one of claims 1 to 6, comprising the steps of: (a) preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure directing agent (Q), a fluoride (F) source, and a hydroxide ion (OH) source; (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100°C to 200°C for a time sufficient to form crystals of the aluminosilicate zeolite; and (c) recovering at least a portion of the aluminosilicate zeolite from step (b). Including, The structure directing agent (Q) is selected from the group consisting of the 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation of formula IIIa, the 1,2,3-trimethyl-5,6,7,8-tetrahydropyrazolo[1,2-a]pyridazin-4-ium cation of formula IIIb, and the 5,6,7-trimethyl-2,3-dihydro-1H-pyrazolo[1,2-a]pyrazol-4-ium cation of formula IIIc: 【Chemistry 2】 The method of claim 1, further comprising the step of:

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

12. 11. The method of claim 10, wherein the synthesis mixture has the following composition in terms of molar ratio: 【Table 4】

13. A process for converting an organic compound to a conversion product comprising contacting the organic compound with the aluminosilicate zeolite of any one of claims 1 to 6.

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