EMM-63 Aluminosilicate Zeolite, Synthesis, and Applications

Abstract

An aluminosilicate zeolite designated EMM-63 characterized by a unique powder XRD pattern or unique connectivity, its preparation method, and its uses.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 261,474, filed September 22, 2021, which is incorporated by reference herein in its entirety.

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

[0003] Background of the Disclosure Both natural and synthetic molecular sieve materials can be used as adsorbents and have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AlPO, 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. Numerous cavities may exist within certain molecular sieve materials, which may be interconnected by numerous channels or pores. These cavities and pores are uniform in size within certain molecular sieve materials. Because the dimensions of these pores are such that they adsorb molecules of a certain size while rejecting molecules of larger sizes, these materials have become known as "molecular sieves" and are utilized in various industrial processes, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0004] Molecular sieves for catalytic and adsorption applications include either naturally occurring or synthetic crystalline molecular sieves. Examples of these molecular sieves include large pore zeolites, medium 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 Zeolite Nomenclature Commission. According to this classification, framework zeolites and other crystalline microporous molecular sieves whose structures have been established are assigned three-letter codes and are described in Ch. Baerlocher, LB et al., Atlas of Zeolite Framework Types, Elsevier, 6th Edition, 2007, which is incorporated herein by reference. These zeolites and their isotypes are also described in the Database of Zeolite Structures of IZA Structure Commission. Large pore zeolites generally have pore sizes of at least about 7 Å and include LTL, VFI ("extra large" 18R), MAZ, FAU, OFF, *Examples of large (or extra-large) pore zeolites include mazzite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and beta. Medium pore zeolites generally have a pore size of about 5 Å to less than about 7 Å, such as MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites. Examples of medium pore zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, and silicalite 2. Small pore zeolites have a pore size of about 3 Å to less than about 5.0 Å, such as CHA, RTH, ERI, KFI, LEV, SOD, and LTA framework type zeolites. 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.

[0005] The ideal inorganic framework structure of a zeolite is a silicate framework in which every tetrahedral atom is bonded to the next four tetrahedral atoms by an oxygen atom. The term "silicate" as used herein refers to a material that contains at least silicon and oxygen atoms (i.e., -O-Si-O-Si-) bonded in alternation, and optionally contains other atoms, such as boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc), within the inorganic framework structure. Atoms other than silicon and oxygen in framework silicates occupy some of the lattice sites occupied by silicon atoms in "all-silica" framework silicates. Thus, the term "framework silicate" as used herein refers to an atomic lattice that contains 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 (or channels) present within it. The size of the pores or channels determines the type of processes a particular zeolite can be applied to. Currently, over 200 unique zeolite framework silicate structures are known and recognized by the International Zeolite Association's Structure Committee, which defines the various pore shapes and orientations.

[0007] Zeolite framework silicates are generally characterized in terms of their ring size, where ring size refers to the number of silicon atoms (or alternative atoms such as those listed above) that are tetrahedrally coordinated with oxygen atoms in the loops to define (or 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 can be symmetrical or asymmetrical, depending on the various structural constraints present in a particular framework silicate.

[0008] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthesis mixture that contains sources of all elements present in the zeolite, such as a source of 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 promote the formation of the molecular sieve and acts as a template around which a particular molecular sieve structure is formed, thereby promoting the formation of the desired molecular sieve. A variety of compounds, including various types of quaternary ammonium cations, have been used as structure directing agents. Typically, zeolite crystals form around a structure directing agent, and once crystallization is complete, the structure directing agent occupies the pores within the zeolite. Thus, since the "as-synthesized" zeolite contains the structure directing agent within its pores, following crystallization, the "as-synthesized" zeolite is usually subjected to a processing step, such as, for example, 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 new internal pore structures that improve selectivity in these processes. Summary of the Invention [Means for solving the problem]

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

[0011] In a first embodiment, the present disclosure provides, in as-fired form (e.g., with at least a portion of the SDA removed), at least 10, or 12, or 14, or 16, or preferably 100% by mass of the sintered product as shown in Table 1: [Table 1] The present invention relates to an aluminosilicate zeolite having an X-ray diffraction pattern including all of the peaks at degrees 2θ selected from the group consisting of

[0012] In a second embodiment, the present disclosure provides, in as-synthesized form (e.g., without SDA removal), at least 10, or 12, or 14, or preferably 10, 12, or 14, 10, or 15, 16, or 17, amino acids, as shown in Table 2: [Table 2] The present invention relates to an aluminosilicate zeolite having an X-ray diffraction pattern that includes all peaks at degrees 2θ selected from the group consisting of:

[0013] In a third embodiment, the present disclosure relates to an aluminosilicate zeolite having (whether in as-synthesized, as-treated (e.g., with acid or acid and steam) and / or as-calcined form) (a) a structure with an orthorhombic space group Pmma with unit cell dimensions a=22.1±0.20 Å, b=7.4±0.20 Å, and c=11.8±0.20 Å, and (b) a structure with a 10×8×8 channel system, with a 10-ring pore along the c-axis having dimensions of 5.2±0.20 Å×4.9±0.20 Å, an 8-ring pore along the c-axis having dimensions of 4.7×0.20 Å×3.1×0.20 Å, and another 8-ring pore in the xz-plane having dimensions of 4.7×0.20 Å×3.1×0.20 Å.

[0014] In a fourth embodiment, the present disclosure provides a method for the preparation of a cellulose acylate comprising the steps of: (a) preparing a cellulose acylate having a molecular weight of 1000 or more; and (b) preparing a cellulose acylate having a molecular weight of 1000 or more; and (c) preparing a cellulose acylate having a molecular weight of 1000 or more; [Table 3] The present invention relates to aluminosilicate zeolites having a framework defined by the connectivity of tetrahedral (T) atoms connected by bridging atoms within the unit cell of

[0015] In a fifth embodiment, the present disclosure relates to a method for producing an aluminosilicate zeolite, comprising the steps of: (a) providing water, a silica source, an alumina source, a potassium source, a hydroxide ion (OH) source, and a zeolite having formula III: [ka] [In the above formula (III), n is 3] (b) heating the synthesis mixture under crystallization conditions comprising a temperature between 100° C. and 200° C. for a sufficient time 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).

[0016] In a sixth embodiment, the present disclosure relates to a method for converting an organic compound to a conversion product, the method comprising contacting the organic compound with an aluminosilicate zeolite according to the first, second, third or fourth embodiment, or prepared according to the method of the fifth embodiment.

[0017] These and other features and attributes of the present disclosure, and their advantageous applications and / or uses, will become apparent from the following detailed description. It will, of course, be understood that features described in connection with one aspect of the invention can be incorporated in other aspects of the invention. In particular, any two or more features described herein, including in this summary section, can be combined to form a combination of features not specifically described herein. [Brief description of the drawings]

[0018] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] FIG. 1 shows the powder XRD pattern of the as-calcined product of Example 1.

[0019] [Diagram 2] FIG. 2 shows an SEM image of the as-synthesized product of Example 1.

[0020] [Diagram 3] FIG. 3 shows an SEM image of the as-synthesized product of Example 3.

[0021] [Figure 4] FIG. 4 shows an SEM image of the as-synthesized product of Example 4.

[0022] [Diagram 5] FIG. 5 shows the SEM image of the as-synthesized product of Example 5.

[0023] [Figure 6] FIG. 6 shows the powder XRD of the as-calcined products of Examples 2, 4 and 5.

[0024] [Figure 7] FIG. 7 shows the crystal structure of EMM-63 as determined from electron diffraction.

[0025] [Figure 8] FIG. 8 shows the powder XRD patterns of the as-synthesized, as-calcined, and ammonium-exchanged versions of the product of Example 7. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Detailed Description The present disclosure relates to an aluminosilicate zeolite, sometimes referred to as EMM-63 zeolite or EMM-63 material, its method of manufacture, and uses thereof.

[0027] The "as-synthesized" (or "as-produced") aluminosilicate zeolites of the present disclosure (i.e., before heat treatment or other treatment to remove SDA from the pores) typically contain SDA, one of the components of the synthesis mixture, within the pores. Aluminosilicate zeolites of the present disclosure from which some or all of the structure directing agent (SDA) has been removed (e.g., by heat treatment or other treatment to remove SDA from the pores) are at least partially calcined, or "as-calcined" materials.

[0028] In a first embodiment, the present disclosure provides, in as-fired form (e.g., with at least a portion of the SDA removed), a cellulose acylate having a molecular weight of 1000 or more and a molecular weight of 1000 or more, as shown in Table 1: [Table 4] The present invention relates to an aluminosilicate zeolite having an X-ray diffraction pattern that includes at least 10, or 12, or 14, or 16, or preferably all, of the peaks at degrees 2θ selected from the group consisting of:

[0029] In a further embodiment, the aluminosilicate zeolite, in its as-calcined form, has the structure shown in Table 1A: [Table 5] and d-spacing values ​​selected from the range of 0.20 degrees 2-theta, where the d-spacing values ​​have a deviation determined based on a corresponding deviation of ±0.20 degrees 2-theta when converted to corresponding values ​​of d-spacing using Bragg's law.

[0030] The XRD patterns with XRD peaks described herein use Cu(Kα) radiation.

[0031] In one or more further embodiments, the aluminosilicate zeolite, in its as-calcined form, may have a micropore volume of from 0.10 to 0.30 cc / g, or from 0.12 to 0.20 cc / g, for example, 0.16 cc / g.

[0032] In one or more further embodiments, the aluminosilicate zeolite is in as-calcined form and has a calcination time of 250 to 700 ml. 2 / g, or 300-600m 2 / g, e.g. 350-500m 2 / g, e.g., 444m 2 / g BET surface area.

[0033] In one or more further embodiments, the aluminosilicate zeolite is in as-calcined form, and optionally has Formula I: [ka] [In the above formula I, 0.05≦m≦0.17] The oxygen atoms in formula I may be replaced by carbon atoms (e.g., in the form of CH2), which may come from the source of the components used to prepare the as-produced aluminosilicate zeolite. The oxygen atoms in formula I may also be replaced by nitrogen atoms, for example, after SDA has been removed. Formula I may represent the framework of a typical aluminosilicate zeolite defined in this disclosure in as-calcined form, and is not meant to be the only representation of said aluminosilicate zeolite. The aluminosilicate zeolite, in as-calcined form, may contain SDA and / or impurities after appropriate treatment to remove SDA and impurities, which are not taken into account in formula I. Furthermore, I does not include protons and charge compensation ions that may be present in the as-calcined aluminosilicate zeolite.

[0034] The variable m is the ratio of Al2O3 to SiO in Equation I. 2 For example, when m is 0.05, the molar ratio of SiO2 to Al2O3 is 20 and the molar ratio of Si to Al is 10. m can vary from 0.05 to 0.17, such as at least 0.06 to a maximum of 0.1, such as a maximum of 0.08, such as 0.06 or 0.07. The molar ratio of Si to Al can be 3 to 10, such as at least 5, or at least 6, and up to 9, or up to 8, or 7 or 8.

[0035] In one or more further embodiments, the aluminosilicate zeolite, in its as-calcined form, may contain potassium ions in a K to Al molar ratio of 0.5 to 1.0, such as 0.7 to 0.9.

[0036] In a second embodiment, the present disclosure provides aluminosilicate zeolites, particularly in their as-synthesized form (e.g., without SDA removal), as shown in Table 2: [Table 6] The aluminosilicate zeolite as defined in the first embodiment has an X-ray diffraction pattern including at least 10, or 12, or 14, or preferably all, peaks in degrees 2θ selected from

[0037] In a further embodiment, the aluminosilicate zeolite is in its as-synthesized form, as shown in Table 2A: [Table 7] and wherein the d-spacing values, when converted to corresponding values ​​of d-spacing using Bragg's law, have a corresponding deviation determined based on ±0.20 degrees 2θ.

[0038] The XRD patterns with XRD peaks described herein use Cu(Kα) radiation.

[0039] In one or more further embodiments, the aluminosilicate zeolite is in as-synthesized form, optionally having the formula II: [ka] [In the formula II, 0≦q≦0.2 and 0.05≦m≦0.17, and Q is a group represented by the formula III: [ka] (wherein n is 3), for example, a tetramethylpyridinium cation selected from the group consisting of N,2,3,5-tetramethylpyridinium, N,2,4,6-tetramethylpyridinium, and mixtures thereof. Formula II may represent the framework of an exemplary aluminosilicate zeolite as defined in this disclosure in its as-synthesized form, thus including the structure directing agent (Q), and is not intended to be the only representation of such materials. The aluminosilicate zeolite, in its as-synthesized form, may contain impurities not accounted for in Formula II. Additionally, Formula II does not include protons and charge compensating ions that may be present in the as-synthesized aluminosilicate zeolite.

[0040] The variable m represents the relationship between the molar ratio of Al2O3 and SiO2 in Formula II. The value of the variable m in Formula II is the same as described herein with respect to Formula I.

[0041] The variable q represents the molar relationship between Q and SiO2 in formula II. For example, when q is 0.1, the molar ratio of Q to SiO2 is 0.1. The molar ratio of Q to SiO2 can vary from 0 to 0.2, such as from 0.02 to 0.1, such as from 0.03 to 0.06.

[0042] In a third embodiment, the present disclosure relates to an aluminosilicate zeolite, in particular an aluminosilicate zeolite as defined in the first and / or second embodiment (whether in as-synthesized, as-treated (e.g., with acid or acid and steam) and / or as-calcined form), having (a) an orthorhombic space group Pmma with unit cell dimensions a=22.1±0.20 Å, b=7.4±0.20 Å, and c=11.8±0.20 Å, and (b) a structure having a 10×8×8 channel system, in which a 10-ring pore has dimensions of 5.2±0.20 Å×4.9±0.20 Å along the c-axis, an 8-ring pore has dimensions of 4.7±0.20 Å×3.1±0.20 Å along the c-axis, and another 8-ring pore in the xz-plane has dimensions of 4.7±0.20 Å×3.1±0.20 Å.

[0043] In a fourth embodiment, the present disclosure provides an aluminosilicate zeolite, in particular a zeolite having a tetrahedral (T) atom structure connected by bridging atoms in the unit cell, as shown in Table 3: [Table 8] The present invention relates to an aluminosilicate zeolite as defined in the first, second and / or third embodiment (whether in as-synthesized, as-treated (e.g., with acid or acid and steam) and / or as-calcined form), having a framework defined by a connectivity of:

[0044] The connectivity can be determined by using the public domain software TOTOPOL by MMJTreacy et al. "The Database of Zeolite Structures of IZA Structure Commission" (see, e.g., MMJTreacy et al., (2004) Microporous and Mesoporous Materials, v.74, pp121-132). The tetrahedral atoms can include one or more elements selected from B, Al, Fe, Ga, Si, Ge, Sn, Ti, Zr, or mixtures thereof. For example, the tetrahedral atoms can be selected from B, Al, or Si, or mixtures thereof. For example, the tetrahedral atoms can include Si or Al. The bridging atoms can be selected from O, N, and C, or mixtures thereof. The bridging atoms can include 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 can 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 the SDA has been removed.

[0045] The aluminosilicate zeolite defined in the first, second, third and / or fourth embodiment may have a Si / Al molar ratio of 3-10, preferably 5-9.

[0046] In a fifth embodiment, the present disclosure provides a method for producing an aluminosilicate zeolite, in particular comprising the steps of: (a) reacting a mixture of water, a silica source, an alumina source, a potassium source (K), a hydroxide ion (OH) source, and a mixture of compounds of Formula III: [ka] [In the above formula III, n is 3] preparing a synthesis mixture containing a structure directing agent (Q) selected from the tetramethylpyridinium cations (b) heating the synthesis mixture under crystallization conditions including a temperature between 100° C. and 200° C. for a sufficient time 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); The present invention relates to a method for producing an aluminosilicate zeolite as defined in the first, second, third and / or fourth embodiment, comprising:

[0047] The structure directing agent (Q) can be at least one of any tetramethylpyridinium cations defined by the formula above, such as N,2,3,4- or N,2,3,5- or N,2,3,6-tetramethylpyridinium, for example, the structure directing agent (Q) can be selected from the group consisting of N,2,3,5-tetramethylpyridinium, N,2,4,6-tetramethylpyridinium, and mixtures thereof. The structure directing agent (Q) can be present in any suitable form, such as a halide, such as a chloride or bromide, a hydroxide, or a nitrate, for example in the form of its hydroxide. The structure directing agent (Q) can be present in the synthesis mixture in a Q / Si molar ratio of 0.05 to 1.0, such as 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 0.5, for example 0.3.

[0048] The synthesis mixture comprises at least one silica source.Suitable silica sources (e.g., silicon oxide sources) include silicates, such as 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, and aqueous colloidal suspensions of silica, such as those sold under the trade name Ludox by EI du Pont de Nemours and Aerodisp by Evonik, preferably including silicates, fumed silicas, precipitated silicas, alkali metal silicates, colloidal silicas, especially aqueous colloidal suspensions of silica.

[0049] The synthesis mixture includes at least one alumina source. Suitable alumina sources (e.g., aluminum oxide sources) include aluminum salts, particularly water-soluble salts such as aluminum sulfate, aluminum nitrate, and aluminum hydroxide, alkali metal aluminates such as sodium aluminate and potassium aluminate, and aluminum alkoxides such as aluminum isopropoxide, 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, and aluminum hydroxide, and alkali metal aluminates such as sodium aluminate and potassium aluminate.

[0050] Instead of or in addition to the aforementioned Si and Al sources, sources containing both Si and Al elements can also be used. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gel or dry silica-alumina powder, silica-alumina, clays such as kaolin, metakaolin, and zeolites, particularly aluminosilicates such as synthetic faujasite and ultrastable faujasite, such as ultrastable Y (USY), beta, or other large to medium pore zeolites.

[0051] The synthesis mixture may have a Si / Al molar ratio of 1-50, such as 5-25, such as 5-15, such as 10.

[0052] The synthesis mixture comprises at least one potassium (K) source. Suitable potassium sources include potassium hydroxide, potassium aluminate, potassium silicate, potassium salts such as KCl or KBr, or potassium nitrate, such as potassium hydroxide. Potassium may also be present in one or more alumina sources, such as potassium aluminate, and / or in one or more silica sources, such as potassium silicate. The synthesis mixture may comprise a potassium source in a K / Si molar ratio of 0.05 to 1.0, such as 0.1 to 1.0, such as 0.15 to 0.5, such as 0.3.

[0053] The synthesis mixture comprises at least one hydroxide ion (OH) source. For example, hydroxide ions can be present as counterions of the structure directing agent (Q) and / or potassium and / or any alkali or alkaline earth metal cation different from potassium (M) and / or by using aluminum hydroxide as the Al source. A suitable hydroxide ion source can also be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof, in particular potassium hydroxide. The synthesis mixture can comprise a hydroxide ion source with an OH / Si molar ratio of 0.1 to 1.5, for example 0.15 to 1.2 or 0.25 to 0.8, for example 0.6.

[0054] The synthesis mixture may optionally contain at least one alkali or alkaline earth metal cation (M) different from potassium. When present, M is preferably selected from the group consisting of sodium, lithium, rubidium, calcium, magnesium and mixtures thereof, preferably sodium. When present, the sodium source may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or a sodium salt, such as, for example, NaCl, NaBr, or sodium nitrate. When present, the lithium source may be lithium hydroxide, or a lithium salt, such as, for example, LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. When present, the rubidium source may be rubidium hydroxide, or a rubidium salt, such as, for example, 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 cation (M) may be present in one or more alumina sources, such as, for example, sodium aluminate, and / or in one or more silica sources, such as, for example, sodium silicate. The synthesis mixture may comprise a source of alkali and / or alkaline earth metal cation (M) in an M / Si molar ratio of 0 to 1.5, such as from 0 or 0.05 to 1.0 or 0.8, such as 0. Alternatively, the synthesis mixture may not comprise any alkali or alkaline earth metal cation (M) different from potassium.

[0055] The synthesis mixture may also optionally contain at least one halide ion source (W), which may be selected from the group consisting of fluoride, chloride, bromide or iodide. The halide ion source (W) may be any compound capable of releasing halide ions in the molecular sieve synthesis mixture. Non-limiting examples of halide ion sources include, for example, hydrogen fluoride, ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), hydrogen chloride, ammonium chloride, hydrogen bromide, ammonium bromide, hydrogen iodide, and ammonium iodide, ammonium halides; salts containing one or several halide ions, such as metal halides, preferably the metal is sodium, potassium, calcium, magnesium, strontium or barium; 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 even 0. If fluoride ions are present in the synthesis mixture, said fluoride ions (F) may be present in a F / Si molar ratio of 0 to less than 0.1, such as 0 to 0.05, or even 0. Alternatively, the synthesis mixture may not comprise a source of halide ions (W), in particular at least no source of fluoride ions.

[0056] The synthesis may be carried out without the addition of nucleation seeds. If nucleation seeds are added to the synthesis mixture, the seeds may be of the same structure as the aluminosilicate zeolite or EMM-63 material of the present disclosure from a previous synthesis or of a different structure, and may suitably be present in an amount of about 0.01 ppm to about 10,000 ppm by weight based on the weight of the synthesis mixture, for example, about 100 ppm to about 5,000 ppm by weight of the synthesis mixture.

[0057] The synthesis mixture typically contains water with a H2O / Si molar ratio of 1-100, such as 15-80, such as 20-50, such as 30. Depending on the nature of the components in the base mixture, an amount of solvent (e.g., water from the hydroxide solution, and optionally methanol and ethanol from hydrolysis of the silica source) of the base mixture may be removed so that the desired solvent to Si molar ratio is achieved in 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 evaporation by spray drying or freeze drying. If too much water is removed during the solvent removal process, water may be added to the resulting mixture to achieve the desired H2O / Si molar ratio. In some instances, if the preparation has a sufficient H2O / Si molar ratio, water does not need to be removed.

[0058] Carbon in the form of CH2 is present in various component sources, such as silica or alumina sources, used to prepare the aluminosilicate zeolites of the present disclosure and can be incorporated into the aluminosilicate zeolite framework as a bridging atom. After the SDA is removed, nitrogen atoms can be incorporated into the aluminosilicate zeolite framework as a bridging atom.

[0059] In one or more embodiments, the synthesis mixture after solvent adjustment (e.g., when a desired water-to-silica ratio is achieved) can be mixed by a mechanical process such as stirring or high shear mixing to ensure proper homogenization of the base mixture, for example, using a dual asymmetric centrifugal mixer (e.g., a FlackTek Speed ​​Mixer) at a mixing speed of 1000 rpm to 3000 rpm (e.g., 2000 rpm).

[0060] The synthesis mixture is then subjected to suitable crystallization conditions for the formation of the aluminosilicate zeolite. Crystallization of the aluminosilicate zeolite may be carried out under static or stirred conditions in a suitable reaction vessel, such as, for example, a Teflon-lined or stainless steel autoclave placed in a convection oven maintained at a suitable temperature.

[0061] The crystallization in step (b) of the method is typically carried out at a temperature between 100°C and 200°C, such as between 110°C and 170°C, for example between 120°C and 150°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 to 100 days, such as between 1 to 50 days, for example between 1 to 30 days, for example at least 1 day, or at least 5 days and up to 15 or 10 days. The crystallization time may be established by methods known in the art, such as, for example, by sampling the synthesis mixture at various time points and measuring 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.

[0062] Typically, the aluminosilicate zeolite is formed in solution and can be recovered by standard means such as centrifugation or filtration. The separated aluminosilicate zeolite can be washed, recovered by centrifugation or filtration, and dried.

[0063] The aluminosilicate zeolites of the present disclosure, when used as adsorbents or catalysts in organic compound conversion processes, can 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 periods of 30 minutes to 48 hours. Dehydration can also be achieved at room temperature by simply placing the molecular sieve in a vacuum, but long periods of time are required to obtain sufficient dehydration.

[0064] 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 treatment or other treatment to remove some or all of the SDA incorporated into the pores during synthesis. Heat treatment (e.g., calcination) of the as-synthesized aluminosilicate zeolite typically involves subjecting the material to a high temperature sufficient to remove some or all of the SDA in an atmosphere selected from air, nitrogen, ozone, or mixtures thereof in a furnace. Although subatmospheric pressures can also be used for the heat treatment, atmospheric pressure is preferred for convenience. Heat treatment may 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 that of the ambient environment of the sample. Heat treatment (e.g., calcination) may be carried out in a box furnace in dry air exposed to a drying tube containing a desiccant that removes water from the air. Heating is typically performed for at least 1 minute, generally for no more than 1 day, or for up to several days. Heating may be performed initially under a nitrogen atmosphere, followed by switching the atmosphere to air and / or ozone.

[0065] Aluminosilicate zeolites may also be subjected to an ion exchange treatment, for example with aqueous ammonium salts such as ammonium nitrate, ammonium chloride, and ammonium acetate, to remove residual alkali metal cations and / or alkaline earths and replace them with protons, thereby producing the acid form of the molecular sieve. To the desired extent, the original cations of the as-synthesized material, such as alkali metal cations, may be replaced by ion exchange with other cations. Preferred replacement cations include, for example, hydrogen ions, hydrogen precursors, such as ammonium ions, and mixtures thereof. The ion exchange step may be performed after the as-produced molecular sieve is dried. The ion exchange step may be performed either before or after the calcination step.

[0066] The aluminosilicate zeolites may also be subjected to other treatments, such as, for example, steaming and / or washing with solvents, which are well known to those skilled in the art and are carried out to modify the properties of the molecular sieve as desired.

[0067] The aluminosilicate zeolites of the present disclosure from which some or all of the SDA has been removed may be used in a wide variety of hydrocarbon conversions, such as the conversion of organic compounds to converted products as adsorbents or as catalysts or catalyst supports. Thus, in a sixth embodiment, the present disclosure relates to the use of the aluminosilicate zeolites described herein as adsorbents or as catalysts or catalyst supports in hydrocarbon conversions. The present disclosure also relates to a method for converting organic compounds to converted products comprising contacting the organic compounds with the aluminosilicate zeolites described herein.

[0068] The aluminosilicate zeolite of the present disclosure (from which some or all of the SDA has been removed) can be used as an adsorbent, for example, to separate at least one component from a mixture of components in a gas or liquid phase having different sorption properties with respect to the feedstock. Thus, at least one component can be partially or substantially completely separated from a mixture of components having different sorption properties with respect to the aluminosilicate zeolite by contacting the mixture with said aluminosilicate zeolite to selectively sorb 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 can be contacted with a sorbent comprising an aluminosilicate zeolite of the present disclosure under effective sorption conditions, thereby forming a sorption product and an effluent product. The one or more desired components are recovered from either the sorption product or the effluent product.

[0069] 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 are 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 may be catalyzed by the aluminosilicate zeolites described herein include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, transalkylation, dealkylation, hydrodecylation, disproportionation, oligomerization, dehydrocyclization, methanol to olefins, deNOx applications, and combinations thereof. The conversion of the hydrocarbon feedstock may be carried out in any convenient manner, such as, for example, a fluidized bed, moving bed, or fixed bed reactor, depending on the type of process desired.

[0070] The aluminosilicate zeolites of the present disclosure may be formulated into a product composition in combination with other materials, such as, for example, binders and / or matrix materials, that impart additional hardness to the final product (or end product). These other materials may be inert materials or catalytically active materials.

[0071] 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 used during use. Such materials include, for example, synthetic or natural zeolites, as well as inorganic materials such as clays, silica and / or metal oxides, such as, for example, alumina, and mixtures thereof. The metal oxides may be naturally occurring or may be in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. The use of resistant materials in combination with the aluminosilicate zeolites of the present disclosure, i.e., crystalline active, combined therewith, or present during the synthesis of the as-produced aluminosilicate zeolite, tends to alter the conversion rate and / or selectivity of the catalyst in certain organic conversion processes. Inert resistant materials function well 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 the use of other means to control the reaction rate. These materials may be incorporated, for example, into natural 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 powder-like materials, so a catalyst with good crush strength can be beneficial.

[0072] Naturally occurring clays that can be used include the montmorillonite and kaolin families, including sub-bentonites and kaolins commonly known as Dixie clay, McNamee clay, Georgia clay, and Florida clay, or others in which the major mineral component is halloysite, kaolinite, dickite, nacrite, or anoxicite. Such clays can be used 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.

[0073] 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, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia.

[0074] These binder materials are resistant to temperature 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 containing a binder. They are typically bound by forming tablets, spheres, or extrudates. The extrudates are typically 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 performed. The molecular sieve may optionally be sized to a thickness of at least 100 m. 2 / g, e.g. at least 200m 2 / g, possibly at least 300m 2 The binder may have a surface area of ​​1.0 g / g.

[0075] The relative proportions of aluminosilicate zeolite and inorganic oxide matrix can vary widely, with the aluminosilicate zeolite content ranging from about 1% to about 100% by weight, more typically from about 2 percent to about 95 percent by weight, and optionally from about 20 percent to about 90 percent by weight of the composite, especially when the composite is prepared in the form of an extrudate.

[0076] The aluminosilicate zeolite of the present disclosure may 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, which performs the hydrogenation-dehydrogenation function. Such hydrogenation components may 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 intimately mixed physically with it. Such components may also be impregnated into or on the aluminosilicate zeolite, for example, by treating a 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, for example, chloroplatinic acid, platinic chloride, and platinum amine complexes. Combinations of metals and their methods of introduction may also be used.

[0077] Those skilled in the art will appreciate that the aluminosilicate zeolites of the present disclosure may contain impurities such as, for example, amorphous materials, unit cells with different topologies (e.g., quartz or molecular sieves of different framework types, which 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 or zeolites of different framework types that coexist with the aluminosilicate zeolites of the present disclosure include ZSM-12, mordenite, cristobalite, quartz, zeolite L, merlinoite, edingtonite, and / or ferrierite. 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 zeolite contains small amounts (less than 50 wt%) of such 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 0.1 wt%), where the weight percent (wt%) value is based on the combined weight of the impurities and the pure aluminosilicate zeolite. The amount of impurities can be suitably determined by powder XRD, rotational electron diffraction, and / or SEM / TEM (e.g., different crystal morphologies).

[0078] The aluminosilicate zeolites described herein are substantially crystalline. As used herein, the term "crystalline" refers to the crystalline solid form of a substance, including but not limited to single-component or multi-component crystalline forms (e.g., including solvates, hydrates, and co-crystals). Crystallinity can mean that the molecules have a regularly repeating and / or ordered arrangement and have 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, for example, XRD (e.g., powder XRD). Other characterization methods known to those skilled in the relevant art can further help identify the crystalline form and also help determine the stability and solvent / water content. As used herein, the term "substantially crystalline" means that the majority (greater than 50% by weight) of the weight of a sample of the described material is crystalline, with the remainder of the sample being in non-crystalline 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), as well as 100% crystallinity (e.g., 0% amorphous form).

[0079] The aspects of the present disclosure will be described in more detail with 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 technology will easily understand that various parameters can be changed or modified to obtain essentially the same results. EXAMPLES

[0080] Working Example The present invention is further described below, but is not intended to limit the scope thereof.

[0081] In these examples, X-ray diffraction (XRD) patterns of the as-synthesized and as-calcined materials were recorded on a powder X-ray diffractometer (Bruker DaVinci D8 Discovery instrument) in continuous mode in the 2θ range of 4° to 36° using Bragg-Brentano geometry with CuKα radiation, Vantec500 detector. Interplanar spacing, d-spacing, is calculated in angstroms, and the relative intensity of the lines, I / Io, 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 in 2theta, and the relative peak area intensity of the lines, I / I(o), (Io being the intensity of the most intense line above background), were determined using the MDI Jade peak search algorithm. It should be understood that the diffraction data listed as single lines may consist 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 involve small changes in unit cell parameters and / or changes in crystal symmetry without altering framework connectivity. These small effects, including changes in relative intensity, may also appear as a result of differences in cation content, framework composition, the nature and degree of pore filling, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0082] Scanning electron microscope (SEM) images of the as-synthesized material were obtained on a Hitachi 4800 scanning electron microscope. The SEM images were used to assist in the assessment of 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 the formation of relatively small amounts of crystalline impurities that may not be discernible in the XRD pattern of the product.

[0083] The following measurements were performed on the ion-exchanged and calcined samples. For each ion-exchanged and calcined sample, the procedure used was as follows: The as-prepared samples were washed twice with 1 M ammonium nitrate solution and then calcined at 500 °C for 16 h.

[0084] The total BET surface area of ​​the material (S BET ), incorporated herein by reference, S. Brunauer et al., J. Am. Chem. Soc., 1938, vol. 60, 309, uses nitrogen adsorption-desorption at liquid nitrogen temperatures.

[0085] 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 described in Lippens, BC et al., "Studies on the Pore System in Catalysis: The Vt Method," J. Catal., Vol. 4, p. 319 (1965), which describes the micropore volume method and is incorporated herein by reference.

[0086] The alpha value is a measure of the cracking activity of a catalyst and is described in U.S. Patent No. 5,611,110 and U.S. Patent No. 3,354,078, and in Journal of Catalysis, Vol. 4, p. 527 (1965), Vol. 6, p. 278 (1966), Vol. 61, p. 395 (1980), each of which is incorporated herein by reference for its disclosure. The experimental conditions for the tests used herein include a constant temperature of 538° C. and various flow rates as described in detail in Journal of Catalysis, Vol. 61, p. 395.

[0087] The molar ratios and conditions used in the synthesis of Examples 1-9, as well as the resulting products, are detailed below and summarized in Table 4.

[0088] Example 1: Seedless synthesis using N,2,3,5-tetramethylpyridinium EMM-63 was first observed from a synthesis carried out in a 1.5 mL stainless steel reactor rotated at 120 °C for 28 days from a synthesis mixture with the following composition in molar ratios: Si / Al = 10, HO / Si = 30, Q / Si = 0.30, OH / Si = 0.60, K / Si = 0.30, using N,2,3,5-tetramethylpyridinium as the structure directing agent (Q) (hydroxide form, 17.5 wt% solution). Ludox LS-30 (30 wt% colloidal silica suspension) was used as the Si source, aluminum hydroxide (82.6 wt% solid Al(OH)3, the remainder water) was used as the Al source, and KOH (17.5 wt% solution) was used as the K source.

[0089] The product was isolated by centrifugation, resuspending in deionized water, and then centrifuging again. This process was repeated three times, after which the product was dried at room temperature. The as-synthesized material was then calcined to 600°C in a box furnace according to the following procedure. The sample was exposed to nitrogen flow at room temperature for 2 hours, and then the temperature was increased from room temperature to 400°C over 2 hours while kept under nitrogen flow. The temperature was then maintained at 400°C for 15 minutes, after which the atmosphere was switched from nitrogen flow to dry air flow. The temperature was then increased from 400°C to 600°C over 1 hour. The temperature was maintained at 600°C for 2 hours, after which the box furnace was allowed to cool.

[0090] XRD analysis of the as-synthesized and as-calcined materials showed that the material had a unique powder XRD pattern that could not be matched to any known zeolite and was designated as the pure as-synthesized and as-calcined EMM-63 product. Figure 1 shows the powder XRD of the as-calcined material. Figure 2 shows an SEM image of the as-synthesized product.

[0091] Example 2: Seed-free medium-scale synthesis using N,2,3,5-tetramethylpyridinium This example is a medium-scale replica of Example 1 and was synthesized in a 23 mL steel Parr reactor with 1.20 g of SiO2. After heating at 120 °C for 13 days, pure EMM-63 product was obtained in a yield of 0.72 g, as identified by the XRD pattern.

[0092] Example 3: Large-scale synthesis using N,2,3,5-tetramethylpyridinium and seeds This example is a large-scale reproduction of Examples 1 and 2 and was synthesized in a 125 mL steel Parr reactor using 11.6 g of SiO2 in the presence of seeds.

[0093] 40.9 g of water was mixed with 101.5 g of N,2,3,5-tetramethylpyridinium as a structure directing agent (Q) (hydroxide form, 17.5 wt % solution). 76.5 g of Ludox LS-30 (30 wt % colloidal silica suspension), 37.1 g of KOH (17.5 wt %), 3.65 g of aluminum hydroxide (82.6 wt % solid Al(OH)3, the rest water), and 0.23 g of seeds (EMM-63 prepared according to Example 2) were added successively, and the resulting mixture was stirred to form a reaction mixture. The reaction mixture was divided into two portions, and one half was filled into a Teflon liner.

[0094] After heating at 120° C. for 9 days, the product was isolated by centrifugation, resuspended in deionized water, and centrifuged again. This process was repeated three times, after which the product was dried at 90° C. The as-synthesized material was then calcined according to the procedure in Example 1.

[0095] The resulting product was confirmed to be pure EMM-63 as identified by its XRD pattern, with a yield of 5.3 g. Figure 3 shows an SEM image of the as-synthesized product. Elemental analysis by inductively coupled plasma (ICP) method of the as-calcined product showed that the material had a Si / Al atomic ratio of 7.8 and a K / Al atomic ratio of 0.89.

[0096] Examples 4-5: Synthesis at various temperatures using N,2,3,5-tetramethylpyridinium and seeds These examples were carried out under the same conditions as in Example 2, but at 135°C and 150°C, respectively, instead of 120°C, and in the presence of 0.23 g of seeds (EMM-63 prepared according to Example 3) added to the synthesis mixture. was added to the synthesis mixture. After heating at 135 °C and 150 °C for 7 days, respectively, the pure EMM-63 products were obtained in yields of 0.72 g and 0.79 g, respectively, as identified by their XRD patterns. Figures 4 and 5 show the SEM images of each as-synthesized product.

[0097] Figure 6 shows the powder XRD of the as-synthesized materials obtained in Examples 4 and 5 at 135°C and 150°C, respectively, compared to the powder XRD of the as-synthesized material obtained in Example 2 at 120°C. This shows the effect of synthesis temperature on the width of the powder patterns of the products obtained at 120°C, 135°C and 150°C, respectively, with the patterns becoming sharper as the crystal thickness increases with temperature.

[0098] Tables 5 and 6 below show the list of peaks and intensities for the as-synthesized EMM-63 product and the as-calcined EMM-63 product of Example 5, respectively. The powder diffraction data of the as-calcined EMM-63 product can be indexed in the orthorhombic space group Pmma with unit cell dimensions a=22.1±0.20 Å, b=7.4±0.20 Å, and c=11.8±0.20 Å. The framework structure has a 10×8×8 channel system. The 10-ring pore along the c-axis has dimensions 5.2 Å×4.9 Å. The 8-ring pore along the c-axis has dimensions 4.7 Å×3.1 Å. Another 8-ring pore in the xz plane also has dimensions 4.7 Å×3.1 Å. Figure 7 shows the crystal structure of EMM-63 determined from electron diffraction.

[0099] Thermogravimetric analysis (TGA) was performed on the as-synthesized EMM-63 product of Example 5 by heating in air from room temperature to 800°C. The total weight loss was 11.1 wt%. Up to 200°C, there was a loss of 3.8 wt% that could be attributed to water. Above 250°C, there was a loss of 7.3 wt% that could be attributed to the loss of the organic SDA.

[0100] Examples 6-7: Synthesis at various temperatures using N,2,4,6-tetramethylpyridinium and seeds These examples were performed at 135° C. and 150° C., respectively, and were similar to Examples 4-5, except that N,2,4,6-tetramethylpyridinium was used as the structure directing agent (Q) (hydroxide form, 17.5 wt % solution) rather than N,2,4,5-tetramethylpyridinium. After heating for 7 days at 135° C. and 150° C., respectively, pure EMM-63 products were obtained and identified by their XRD patterns.

[0101] The as-synthesized EMM-63 material of Example 7 was calcined according to the procedure defined in Example 1, ammonium ion-exchanged using 1 M ammonium nitrate solution in a batch system, and then calcined again at 500° C. for 16 hours to convert the material to the acidic form. Figure 8 compares the powder XRD patterns of the as-synthesized and as-calcined ammonium-exchanged versions of the EMM-63 product.

[0102] Example 8: Synthesis using N,2,4,6-tetramethylpyridinium and potassium aluminate This example was carried out under the same conditions and with the same molar ratios as in Example 6, except that potassium aluminate (11.2 wt % solution) was used as the Al source rather than aluminum hydroxide. After heating at 135° C. for 7 days, a pure EMM-63 product was obtained, as identified by the XRD pattern.

[0103] Example 9: Large-scale synthesis using N,2,4,6-tetramethylpyridinium and potassium aluminate This example was a larger scale replica of Example 8, synthesized in a 125 mL steel Parr reactor. After heating at 135° C. for 7 days, a pure EMM-63 product was obtained, as identified by the XRD pattern.

[0104] The as-synthesized EMM-63 material was calcined according to the procedure defined in Example 1, ammonium ion-exchanged using 1 M ammonium nitrate solution in a batch system, and then calcined again at 500° C. for 16 h to convert the material to the acidic form.

[0105] The BET surface area (S BET ) is 444m 2 / g, and its micropore volume (V micro ) was 0.16 cc / g, with an alpha value of 48. The uptake of n-hexane, 2,3-dimethylbutane (2,3-DMB), and mesitylene was measured on the ion-exchanged and calcined material. The material was placed under a nitrogen stream, then hydrocarbons were introduced through a sparger to saturate the nitrogen stream, and the uptake of the hydrocarbons was measured. Each hydrocarbon was adsorbed at a different temperature: n-hexane at 90°C, 2,3-DMB at 120°C, and mesitylene at 100°C. The uptake of n-hexane was 46.0 mg / g, that of 2,3-DMB at 47.3 mg / g, and that of mesitylene at 16.8 mg / g. [Table 9] [Table 10] [Table 11] [Table 12] [Table 13]

[0106] 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 recited herein, ranges from any lower limit to any upper limit are contemplated. All numerical values ​​in the detailed description herein are also modified by the indicated value "about" to take into account experimental error and variations expected by those skilled in the art.

[0107] Where the foregoing description refers to integers or elements having known, obvious, or foreseeable equivalents, such equivalents are incorporated herein as if set forth separately. Reference should be made to the claims to determine the true scope of the invention, which should be interpreted to encompass all such equivalents. The reader will also understand that any 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 any such integers or features may be beneficial in some embodiments of the invention, but may be undesirable in other embodiments and therefore may not be present.

[0108] Additionally or alternatively, the present invention relates to:

[0109] Embodiment 1: An aluminosilicate zeolite having, in its as-calcined form, an X-ray diffraction pattern comprising at least 10 peaks selected from Table 1 or Table 1A.

[0110] Embodiment 2: An embodiment of the aluminosilicate zeolite having an X-ray diffraction pattern in as-calcined form that includes at least 12, preferably at least 14, more preferably at least 16, and most preferably all of the peaks selected from Table 1 or Table 1A.

[0111] Embodiment 3: Formula I: [ka] [In the above formula I, 0.05≦m≦0.17] 3. The aluminosilicate zeolite of embodiment 1 or 2 having a molecular formula of:

[0112] Embodiment 4: An aluminosilicate zeolite having, in as-synthesized form, an X-ray diffraction pattern comprising at least 10 peaks selected from Table 2 or Table 2A.

[0113] Embodiment 5: The aluminosilicate zeolite of embodiment 4, having an X-ray diffraction pattern that includes at least 12, preferably at least 14, more preferably all of the peaks selected from Table 2 or Table 2A in as-synthesized form.

[0114] Embodiment 6: Formula II: [ka] [In the formula II, 0≦q≦0.2 and 0.05≦m≦0.17, and Q is a group represented by the formula III: [ka] (In formula III, n is 3.) Preferably, Q is selected from the group consisting of N,2,3,5-tetramethylpyridinium, N,2,4,6-tetramethylpyridinium, and mixtures thereof. 6. The aluminosilicate zeolite of embodiment 4 or 5, having a molecular formula of

[0115] Embodiment 7: The aluminosilicate zeolite of any one of embodiments 1 to 6, having a framework defined by the connectivity defined in Table 3 for the tetrahedral (T) atoms in the unit cell, and the tetrahedral (T) atoms are linked by bridging atoms.

[0116] Embodiment 8: The aluminosilicate zeolite of any one of embodiments 1 to 7, having (a) an orthorhombic space group Pmma with unit cell dimensions a=22.1±0.20 Å, b=7.4±0.20 Å, and c=11.8±0.20 Å, and (b) a structure with a 10×8×8 channel system, in which (b) a 10-ring pore along the c-axis has dimensions of 5.2±0.20 Å×4.9±0.20 Å, an 8-ring pore along the c-axis has dimensions of 4.7±0.20 Å×3.1±0.20 Å, and another 8-ring pore in the xz plane has dimensions of 4.7×0.20 Å×3.1×0.20 Å.

[0117] Embodiment 9: The aluminosilicate zeolite of any one of embodiments 1 to 8, having a Si / Al molar ratio of 3 to 10, preferably 5 to 9.

[0118] Embodiment 10: A pore volume of 0.10 to 0.30 cc / g, preferably 0.12 to 0.20 cc / g, and / or 250 to 700 m 2 / g, or 300-600m 2 / g, e.g. 350-500m 2 The aluminosilicate zeolite of any one of embodiments 1-3 and 7-9 having a BET surface area of ​​100 / g.

[0119] Embodiment 11: A method for producing the aluminosilicate zeolite of any one of embodiments 1 to 9, comprising: (a) water, a silica source, an alumina source, a potassium source, a hydroxide ion (OH) source, and a mixture of compounds of Formula III: [ka] [In the above formula III, n is 3] preparing a synthesis mixture containing a structure directing agent (Q) selected from the tetramethylpyridinium cations (b) heating the synthesis mixture under crystallization conditions including a temperature between 100° C. and 200° C. for a sufficient time 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); The method comprising:

[0120] Embodiment 12: The method of embodiment 11, wherein the structure directing agent (Q) is selected from the group consisting of N,2,3,5-tetramethylpyridinium, N,2,4,6-tetramethylpyridinium, and mixtures thereof, in particular, the structure directing agent (Q) is in the form of its hydroxide.

[0121] Embodiment 13: The synthesis mixture comprises, in terms of molar ratios: [Table 14] 13. The method of embodiment 11 or 12, having a composition of

[0122] Embodiment 14: A method for converting an organic compound to a conversion product, comprising contacting the organic compound with the aluminosilicate zeolite of any one of embodiments 1-10.

Claims

1. In as-fired form, Table 1: 【Table 1】 An aluminosilicate zeolite having an X-ray diffraction pattern including at least 10 peaks selected from:

2. 2. The aluminosilicate zeolite of claim 1, which in its as-calcined form has an X-ray diffraction pattern that includes at least 12, preferably at least 14, more preferably at least 16, and most preferably all, peaks selected from Table 1.

3. Formula I: 【Chemical 1】 [In the formula I, 0.05≦m≦0.17] 2. The aluminosilicate zeolite of claim 1 having the molecular formula:

4. In the as-synthesized form, Table 2: 【Table 2】 An aluminosilicate zeolite having an X-ray diffraction pattern including at least 10 peaks selected from:

5. 5. The aluminosilicate zeolite of claim 4, which in its as-synthesized form has an X-ray diffraction pattern that includes at least 12, preferably at least 14, more preferably all peaks selected from Table 2.

6. Formula II: 【Chemistry 2】 [In the formula (II), 0≦q≦0.2, 0.05≦m≦0.17, and Q is a group represented by the formula III: 【Chemistry 3】 (In the above formula III, n is 3) tetramethylpyridinium cations selected from the group consisting of 5. The aluminosilicate zeolite of claim 4 having the molecular formula:

7. 7. The aluminosilicate zeolite of claim 6, wherein in Formula III, Q is selected from the group consisting of N,2,3,5-tetramethylpyridinium, N,2,4,6-tetramethylpyridinium, and mixtures thereof.

8. Table 3 for tetrahedral (T) atoms in the unit cell: 【Table 3】 3. The aluminosilicate zeolite of claim 1 or 2, having a framework defined by the above connectivity of

9. 3. The aluminosilicate zeolite of claim 1 or 2, having (a) an orthorhombic space group Pmma with unit cell dimensions a=22.1±0.20 Å, b=7.4±0.20 Å, and c=11.8±0.20 Å, and (b) a structure with a 10×8×8 channel system, in which (b) a 10-ring pore has dimensions along the c-axis of 5.2±0.20 Å×4.9±0.20 Å, an 8-ring pore has dimensions along the c-axis of 4.7±0.20 Å×3.1±0.20 Å, and another 8-ring pore has dimensions in the x-z plane of 4.7±0.20 Å×3.1±0.20 Å.

10. 3. An aluminosilicate zeolite according to claim 1 or 2, having a Si / Al molar ratio of 3 to 10, preferably 5 to 9.

11. 3. A method for producing the aluminosilicate zeolite of claim 1 or 2, comprising: (a) comprising water, a silica source, an alumina source, a potassium source, a hydroxide ion (OH) source, and a catalyst having Formula III: 【Chemistry 4】 [In the formula (III), n is 3] preparing a synthesis mixture containing a structure directing agent (Q) selected from the group consisting of the tetramethylpyridinium cations (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100 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); 1. A method for producing an aluminosilicate zeolite, comprising:

12. 12. The method of claim 11, wherein the structure directing agent (Q) is selected from the group consisting of N,2,3,5-tetramethylpyridinium, N,2,4,6-tetramethylpyridinium, and mixtures thereof.

13. 13. The method of claim 12, wherein the structure directing agent (Q) is in the form of its hydroxide.

14. The synthesis mixture has the following molar ratio: 【Table 4】 12. The method of claim 11, comprising:

15. 10. A method for converting an organic compound to a conversion product, comprising contacting the organic compound with the aluminosilicate zeolite of claim 1 or 2.

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