EMM-75 Molecular Sieve Composition, Synthesis and Use

Abstract

A molecular sieve called EMM-75, characterized by a unique powder XRD pattern, its manufacturing method, and its use.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority and benefits of U.S. Provisional Application No. 63 / 492,292, filed on 27 March 2023, which are incorporated herein by reference in their entirety.

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

[0003] Molecular sieve materials, whether natural or synthetic, can be used as adsorbents and may possess catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AlPO, and mesoporous materials, are regularly aligned, porous crystalline materials with a clear crystalline structure measured by X-ray diffraction (XRD). Certain molecular sieves are regularly aligned, creating a distinctive and identifiable XRD pattern. Numerous cavities may exist within certain molecular sieves, and these cavities may be interconnected by many channels or pores. These cavities and pores are uniformly sized within certain molecular sieve materials. Because the dimensions of these pores allow adsorbed molecules of a specific dimension while simultaneously rejecting molecules of a larger dimension, these materials have come to be known as "molecular sieves" and are used in a variety of industrial processes, such as decomposition (or cracking), hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0004] Molecular sieves used for catalysis and adsorption include both naturally occurring and synthetic crystalline molecular sieves. These zeolites and their isotypes are classified by the Structure Commission of the International Zeolite Association in accordance with the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, structurally established skeletal zeolites and other crystalline microporous molecular sieves are assigned a three-letter code and are described in the "Atlas of Zeolite Framework Types" (edited by Ch. Baerlocher, LB et al., Elsevier, 6th edition, 2007), which is incorporated into the specification by reference. These zeolites and their isotypes are also described at http: / / america.iza-structure.org / IZA-SC / ftc_table.php.

[0005] The ideal inorganic framework structure for zeolites is a silicate (or silicate) framework structure, in which all tetrahedral atoms are connected to the four nearest neighboring tetrahedral atoms by oxygen atoms. The term “silicate” as used herein refers to a substance that contains at least silicon and oxygen atoms, which are alternately bonded to each other (i.e., -O-Si-O-Si-), and optionally contains other atoms in the inorganic framework structure, including boron, aluminum, or other metals (such as transition metals like titanium, vanadium, or zinc). In the skeletal silicate (or skeletal silicate), atoms other than silicon and oxygen occupy a portion of the lattice sites, otherwise these lattice sites are otherwise occupied in the same way by silicon atoms as in the “all-silica” skeletal silicate. Thus, as used herein, the term "framework silicate" refers to an atomic lattice containing any of silicates, borosilicates, gallosilicates, ferrisilicates, aluminosilicates, titanosilicates, zincosilicates, vanadosilicates, or similar materials.

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

[0007] Zeolite or molecular sieve skeleton silicates are generally characterized in terms of their ring size, where ring size refers to the number of silicon atoms (or alternative atoms as described above) that tetrahedralize with oxygen atoms in the loop, defining pores or channels within the zeolite. For example, an "8-membered ring" zeolite means a zeolite having pores or channels defined by eight alternating tetrahedral atoms and eight oxygen atoms in the loop. The pores and channels defined within a given zeolite may be symmetrical or asymmetrical, depending on the various structural constraints present in the particular skeleton silicate.

[0008] Zeolites can be classified into small, medium, large, and ultra-large pore structures with respect to pore windows defined by 8, 10, 12, and more than 12 T atoms, respectively. Ultra-large pore zeolites (>12R) include, for example, AET(14R, e.g., ALPO-8), SFN(14R, e.g., SSZ-59), VFI(18R, e.g., VPI-5), CLO(20R, e.g., cloverite), and ITV(30R, e.g., ITQ-37) skeletonized zeolites. Ultra-large pore zeolites generally have a free pore diameter larger than approximately 0.8 nm. Large pore zeolites (>12R) include, for example, LTL, MAZ, FAU, EMT, OFF, *BEA, MOR, and SFS skeletonized zeolites include, for example, mazite, ofretite, zeolite L, zeolite Y, zeolite X, omega, ZSM-2, zeolite T, beta, and SSZ-56. Large-pore zeolites generally have a free pore diameter of 0.6 to 0.8 nm. Medium (or intermediate) pore size zeolites (10R) include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON skeletonized zeolites, for example, ZSM-5, ZSM-11, ZSM-22, MCM-22, silicilite-1, and silicilite-2. Medium-pore size zeolites generally have a free pore diameter of 0.45 to 0.6 nm. Small-pore size zeolites (8R) include, for example, CHA, RTH, ERI, KFI, LEV, and LTA-framed zeolites, such as ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, Zeolite A, Chabazite, and ALPO-17. Small-pore size zeolites generally have a free pore diameter of 0.3 to 0.45 nm.

[0009] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthesis mixture, which contains sources of all elements present in molecular sieves (or zeolites), such as alumina as well as silica. Often, a structure-directing agent (SDA) is also present. A structure-directing agent is a compound thought to promote molecular sieve formation, acting as a template. This template can cause the formation of specific molecular sieves around it, thereby promoting the formation of the desired molecular sieve. Various compounds are used as structure-directing agents, including various forms of quaternary ammonium cations. Typically, molecular sieve (or zeolite) crystals form around the structure-directing agent, and once crystallization is complete, the structure-directing agent occupies the pores within the molecular sieve. Therefore, "as-synthesized" (or "as-made") molecular sieves contain structure-directing agents within their pores, and after crystallization, "as-synthesized" molecular sieves are typically subjected to processing steps such as calcination to remove the structure-directing agents.

[0010] While many different molecular sieves have been discovered, there is still a need for novel molecular sieves (or zeolites) with desired properties for gas separation and drying, organic conversion reactions, and other applications. Novel molecular sieves can contain novel internal pore structures, which can improve selectivity in these processes. Furthermore, identifying novel structure-directing agents and more efficient methods for synthesizing molecular sieves is important to facilitate the preparation of new molecular sieves and / or reduce the manufacturing costs of known molecular sieves. [Overview of the Initiative]

[0011] This disclosure relates to molecular sieves, methods for producing the same, and uses thereof.

[0012] In a first aspect, the present disclosure relates to a molecular sieve having an X-ray diffraction pattern that, in a calcined form (e.g., a form in which at least a portion of the SDA has been removed), includes at least 14, at least 15, at least 16, or at least 17, e.g., all, of the peaks (2θ (°)) in Table 1: [Table 1] In a second aspect, the present disclosure relates to a molecular sieve having an X-ray diffraction pattern that, in an as-synthesized form (e.g., a form in which the SDA has not been removed), includes at least 9, at least 10, at least 11, or at least 12, e.g., all, of the peaks (2θ (°)) in Table 2:

[0013] In a third aspect, the present disclosure relates to a method for producing a molecular sieve, particularly a molecular sieve as defined in the first and / or second aspects of the present disclosure, the method comprising the following steps: (a) preparing a synthesis mixture comprising water, a source of a tetravalent element oxide (Y), a source of a trivalent element oxide (X), a structure directing agent (Q) comprising a 2-ethyl-1,3-dimethylbenzimidazolium cation of formula I: [Table 2] In a third aspect, the present disclosure relates to a method for producing a molecular sieve, particularly a molecular sieve as defined in the first and / or second aspects of the present disclosure, the method comprising the following steps: (a) preparing a synthesis mixture comprising water, a source of a tetravalent element oxide (Y), a source of a trivalent element oxide (X), a structure directing agent (Q) comprising a 2-ethyl-1,3-dimethylbenzimidazolium cation of formula I:

[0014] In a third aspect, the present disclosure relates to a method for producing a molecular sieve, particularly a molecular sieve as defined in the first and / or second aspects of the present disclosure, the method comprising the following steps: (a) preparing a synthesis mixture comprising water, a source of a tetravalent element oxide (Y), a source of a trivalent element oxide (X), a structure directing agent (Q) comprising a 2-ethyl-1,3-dimethylbenzimidazolium cation of formula I: [Chemical formula] a fluoride ion source (F), and optionally a source of hydroxide ions (OH); (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 molecular sieve; (c) recovering at least a portion of the molecular sieve from step (b); and (d) optionally treating the molecular sieve recovered in step (c) to remove at least a portion of the structure directing agent.

[0015] In a fourth aspect, the Disclosure relates to a process for converting an organic compound into a conversion product, the process comprising contacting the organic compound with a molecular sieve prepared according to

[0016] These and other features and characteristics of this disclosure, as well as their advantageous applications and / or uses, will become apparent from the detailed description that follows. Of course, features described in relation to one aspect of the invention may be incorporated into other aspects of the invention. In particular, any two or more features described herein, including the outline of the invention, can be combined to form a combination of features not specifically described herein. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 shows the powder XRD pattern of the as-synthesized EMM-75 material from Example 2. [Figure 2] Figure 2 shows the powder XRD pattern of the calcined EMM-75 material from Example 2. [Figure 3] Figure 3 shows an SEM image of the as-synthesized product from Example 2. [Figure 4] Figure 4 shows the structure of the EMM-75 material along the

[0100] direction. [Figure 5] Figure 5 shows the powder XRD patterns of the as-synthesized and calcined EMM-75 material from Example 4. [Figure 6] Figure 6 shows an SEM image of the as-synthesized product from Example 4.

[0018] [Detailed explanation] This disclosure relates to molecular sieve compositions, methods for producing the same, and uses thereof. The molecular sieve may be referred to as EMM-75 molecular sieve, EMM-75 zeolite, or EMM-75 material.

[0019] In a first embodiment, the present disclosure relates to a firing configuration (e.g., a configuration in which at least a portion of the SDA is removed), as shown in Table 1: [Table 3] This relates to molecular sieves having an X-ray diffraction pattern that includes at least 14, at least 15, at least 16, or at least 17 peaks, for example, all of the peaks (2θ(°)).

[0020] In a further embodiment, the molecular sieve is fired in the form shown in Table 1A: [Table 4] A molecular sieve having an X-ray diffraction pattern that includes at least 14, at least 15, at least 16, or at least 17 peaks, for example, all of them, wherein the spacing d (d-spacing) value has a deviation determined based on the corresponding deviation ±0.20(2θ(°)) when converted to a value corresponding to the spacing d using Bragg's law.

[0021] In a further embodiment, the X-ray diffraction pattern of the molecular sieve may include at least 10, at least 11, at least 12, at least 14, or all of the peaks (2θ(°)) in Table 1 or 1A in the fired state, where these peaks have a minimum relative intensity of 10 to 30, for example, the 10 peaks (2θ(°)) in Table 1 or Table 1A have a minimum relative intensity of 20 to 40.

[0022] The XRD patterns having the XRD peaks described herein are Cu(K α ) Use radiation.

[0023] In one or more further embodiments, the molecular sieve is fired in a manner of 0.02 to 0.2 cm 3 / g, for example, 0.05~0.1cm 3 / g, for example, 0.07cm3 It may have a micropore volume of / g.

[0024] In one or more embodiments, the molecular sieve, in its calcined form, has a micropore surface area of 75 to 500 m 2 / g, for example 100 to 300 m 2 / g, for example about 150 to 180 m 2 / g, and / or an external surface area of 10 to 300 m 2 / g, for example 30 to 200 m 2 / g, for example 45 to 155 m 2 It may have an external surface area of / g.

[0025] In one or more further embodiments, the molecular sieve, in its calcined form, optionally has the formula II: (m)X2O3:YO2 (Formula II) It can be represented by the molecular formula, where 0.01 ≤ m ≤ 0.1, X is a trivalent element, and Y is a tetravalent element. Y comprises or may consist of Si and / or Ge, for example, Si or Si. X comprises or may consist of Al and / or B, for example, Al or Al. In embodiments, when Y is Si and X is Al, the molecular sieve is an aluminosilicate. In embodiments, when Y is Si and X is B, the molecular sieve is a borosilicate. The oxygen atom in formula II may be replaced with a carbon atom (e.g., in the form of CH2), which comes from a source of components used to prepare the as-fabricated molecular sieve. Alternatively, the oxygen atom in formula II may be replaced with a nitrogen atom, for example, after SDA has been removed. Formula II can represent the framework of a typical molecular sieve in a calcined form as defined herein, and does not mean that it is the only representation of such molecular sieve. The molecular sieve may contain SDA and / or impurities in the calcined form after appropriate treatment to remove SDA and impurities not described by Formula II. Furthermore, Formula II does not include protons and charge compensation ions that may be present in the calcined molecular sieve.

[0026] The variable m represents the relationship between the molar ratios of YO2 and X2O3 in Equation II. For example, when m is 0.025, the molar ratio of YO2 to X2O3 is 40, and the molar ratio of Y to X is 20 (for example, the molar ratio of Si / Al is 20). m can vary in the range of 0.01 to 0.1, for example at least 0.01 or at least 0.0125, preferably more than 0.0125, at least 0.017 to at most 0.1, at most 0.07, or at most 0.05, for example about 0.025, 0.03, or 0.04. The molar ratio of Y to X may be 5 to 50, for example at least 5, at least 7.5, or at least 10, and at most 50 or at most 40, preferably less than 40, or at most 30, for example about 12.5, 15, or 20.

[0027] In a second aspect, the disclosure relates to molecular sieves, particularly molecular sieves as defined in the first aspect, in their as-synthesized form (e.g., in a form in which the SDA has not been removed), as shown in Table 2: [Table 5] This relates to molecular sieves having an X-ray diffraction pattern that includes at least 9, at least 10, at least 11, or at least 12 peaks, for example, all of the peaks (2θ(°)).

[0028] In a further embodiment, this molecular sieve, in its as-synthesized form, is as shown in Table 2A: [Table 6] The X-ray diffraction pattern has at least 9, at least 10, at least 11, or at least 12 peaks, for example, all of the peaks (2θ(°)), and the interval d value has a deviation determined based on the corresponding deviation ±0.20(2θ(°)) when converted to a value corresponding to the interval d using Bragg's law.

[0029] In a further embodiment, the X-ray diffraction pattern of the molecular sieve may, in its as-synthesized form, include at least six, for example, at least seven, at least eight, or all of the peaks (2θ(°)) in Table 2 or 2A, where these peaks have a minimum relative intensity of 10–20, for example, the nine peaks (2θ(°)) in Table 2 or Table 2A have a minimum relative intensity of 10–40 or 20–40.

[0030] The XRD patterns having the XRD peaks described herein are Cu(K α ) Use radiation.

[0031] In one or more further embodiments, the molecular sieve, in its as-synthesized form, optionally has the molecular formula of formula III: (q)Q:(m)X2O3:YO2 (Formula III) may be represented by, where 0 < q ≦ 0.7, 0.01 ≦ m ≦ 0.1, X is a trivalent element defined by Formula II, Y is a tetravalent element defined by Formula II, and Q is Formula I: [Chemical formula] contains the 2-ethyl-1,3-dimethylbenzimidazolium cation of.

[0032] Formula III can represent the skeleton of a typical molecular sieve as defined in this disclosure in its as-synthesized form. Thus, this molecular sieve contains a structure directing agent (Q), and does not mean that it is the only representation of such a material. This molecular sieve may contain impurities not described by Formula III in its as-synthesized form. Further, Formula III does not include protons and charge compensating ions that may be present in the as-synthesized molecular sieve.

[0033] The variable m represents the relationship of the molar ratio of X2O3 to YO2 in Formula III. The value of the variable m in Formula III is the same as that described herein for Formula II.

[0034] The variable q represents the molar relationship between YO2 and Q in Formula III. For example, when q is 0.1, the molar ratio of Q to YO2 is 0.1. The molar ratio of Q to YO2 may be greater than 0 and not more than 0.7, such as 0.1 to 0.6, such as 0.1 to 0.5.

[0035] In a further embodiment, the as-synthesized molecular sieve of the second aspect of the present disclosure is a layer phase having monoclinic symmetry [e.g., unit cell dimensions a=7.3±0.30 Å, b=17.7±0.30 Å, and c=25.0±0.30 Å, β:~95.0°] and contains silanol defects, e.g., about 17% silanol defects. In a further embodiment, upon firing, the molecular sieve of the first aspect of the present disclosure becomes orthorhombic and more symmetrical [e.g., unit cell dimensions a=7.6±0.30 Å, b=17.9±0.30 Å, and c=22.4±0.30 Å], and the defects are at least partially healed. The calcined molecular sieves of the first aspect of this disclosure have 48 Si atoms in one unit cell and share a structure similar to MOR zeolite, but the 12-membered ring dimension is more elliptical (12MR: 6.5±0.30 Å × 8.3±0.30 Å, compared to 6.5±0.30 Å × 7±0.30 Å for MOR), and the 8-membered ring dimension is narrower (8MR: 5.7±0.30 Å × 2.3±0.30 Å, compared to 5.7±0.30 Å × 2.6±0.30 Å for MOR).

[0036] In further embodiments, at least a portion of the molecular sieve crystals of the present disclosure (whether in as-synthesized or calcined form) may have plate-like forms, particularly thin plate-like forms. When we say that "at least a portion" of the molecular sieve crystals may have (thin) plate-like forms, we mean that at least about 50%, for example, at least 60%, at least 75%, or at least 85% of the molecular sieve crystals may have (thin) plate-like forms. "(Thin) plate-like forms" means a form that is substantially a (thin) platelet, for example, a disc or rectangular plate, wherein the plate has a first and second primary dimension that can be referred to as the length (l) and width (b) of the platelet (i.e., the longest dimension of the platelet's largest face, and the midpoint of this largest face measured perpendicular to the longest dimension), and a secondary third dimension that can be referred to as the thickness (t) of the platelet (i.e., the midpoint of the longest dimension and the smallest dimension measured perpendicular to this largest face). The morphology and the proportion (as vol%) of crystals possessing this morphology can be determined by image analysis, such as scanning electron microscopy (SEM) images, using software such as ImageJ.

[0037] Molecular sieve crystals having a (thin) plate-like morphology according to this disclosure may have a thickness of, for example, about 1 nm, for example at least about 5 nm or 10 nm, and up to about 100 nm, for example up to 50 nm or 25 nm.

[0038] In a third aspect, the Disclosure relates to a method for producing molecular sieves, particularly molecular sieves as defined in the first and / or second aspects of the Disclosure, the method comprising the following steps: (a) Water, a source of tetravalent oxides (Y), a source of trivalent oxides (X), formula I: [ka] A step of preparing a synthetic mixture comprising a structure-directing agent (Q) comprising a 2-ethyl-1,3-dimethylbenzimidazolium cation, a fluoride ion source (F), and optionally a hydroxide ion source (OH); (b) Heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve; (c) A step of recovering at least a portion of the molecular sieve from step (b); and, (d) A step of optionally processing the molecular sieves recovered in step (c) to remove at least a portion of the structural directing agent (Q).

[0039] The structure-directing agent (Q) comprises a 2-ethyl-1,3-dimethylbenzimidazolium cation of formula I, as defined above. The structure-directing agent (Q) may exist in any suitable form, such as a halogenated compound such as a fluoride, chloride, iodide, or bromide, as a hydroxide, or as a nitrate, for example, in the form of the hydroxide. The structure-directing agent (Q) may be present in the synthetic mixture in a Q / Y molar ratio of 0.05 to 1.0, for example 0.1 to 0.8, 0.2 to 0.7, or 0.3 to 0.6, for example 0.5.

[0040] The synthetic mixture comprises at least one oxide source of a tetravalent element Y, where Y can be selected from Si and / or Ge, preferably Si. The suitable source of tetravalent element Y that can be used in the preparation of the synthetic mixture depends on the element Y selected. In embodiments where Y is silicon, suitable Si sources for use in this method (e.g., silicon oxide sources) include silicates, such as tetraalkyl orthosilicates like tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS); fumed silica such as Aerosil® (available from Evonik), Cabosperse® (available from Cabot) and CabO-O-Sil® (available from DMS); precipitated silica such as Ultrasil® and Sipernat® 340 (available from Evonik) or Hi-Sil®; alkali metal silicates such as potassium silicate and sodium silicate; and, for example, EI du Pont de Nemours. This includes aqueous colloidal suspensions of silica, such as those sold under Ludox® by Nemours, or under Aerodisp® by Evonik, preferably silicates, fumed silica, colloidal silica, precipitated silica, alkali metal silicates, and particularly silicates. In embodiments where Y is germanium, a suitable Ge source includes germanium oxide.

[0041] The synthetic mixture comprises at least one oxide source of a trivalent element X, where X can be selected from Al and / or B, particularly Al. Suitable sources of the trivalent element X that can be used in the preparation of the synthetic mixture depend on the selected element X. In embodiments where X is aluminum, suitable Al sources for use in this method (e.g., aluminum oxide sources) include aluminum hydroxide, aluminum salts, particularly water-soluble salts such as aluminum sulfate and aluminum nitrate, alkali metal aluminates such as sodium aluminate, and aluminum alkoxides such as aluminum isopropoxide, as well as hydrated aluminum oxides such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other aluminum sources include, but are not limited to, other water-soluble aluminum salts or aluminum metals such as chipped aluminum. Particularly suitable alumina sources are aluminum hydroxide and aluminum alkoxides. In embodiments where X is boron, the boron source includes boric acid and borates such as sodium tetraborate or borax and potassium tetraborate. Boron sources tend to be more soluble than aluminum sources in hydroxide-mediated synthesis systems.

[0042] In addition to or instead of the Y and X sources described above, sources containing both Y and X, such as Si and Al sources, may also be used. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gel or dried silica-alumina powder, silica-alumina, clays such as kaolin and metakaolin, and zeolites, in particular including synthetic faujasite and ultrastable faujasite, such as Y-type zeolites, Ultrastable Y (USY), beta, or other aluminosilicates such as large-pore to medium-pore molecular sieves or zeolites.

[0043] The synthetic mixture may have a Y / X molar ratio of 5 to 50, for example 7.5 to 40 or less than 40, for example 10 or 12 to 35, 30 or 25, for example 12.5, 15 or 20.

[0044] In a preferred embodiment of this aspect of the invention, Y is Si, X is Al or B, and the molecular sieve is aluminosilicate or borosilicate, in particular Y is Si, X is Al, and the molecular sieve is aluminosilicate.

[0045] The synthetic mixture contains at least one source of fluoride ions (F). The source of fluoride ions (F) may be any compound capable of releasing fluoride ions in the molecular sieve synthetic mixture. For example, the fluoride ion may be present as a counterion of a structure-directing agent (Q). Non-limiting examples of sources of fluoride ions (F) include hydrogen fluoride (HF), salts containing one or more fluoride ions such as metal fluorides, preferably salts where the metal is an alkali metal or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium, or barium, e.g., aluminum (AlF3, Al2F6) or tin (SnF2), ammonium fluoride (NH4F), and ammonium difluoride (NH4HF2). Particularly favorable sources of fluoride ions are HF, NH4F, and NH4HF2, with HF being particularly favored. Furthermore, small amounts of fluoride ions (F) may be present as impurities in any source of alkali metal or alkaline earth metal cations (M), for example. Fluoride ions (F) may be present in F / Y molar ratios of 0.05 to 1.0, for example 0.1 to 0.8, for example 0.15 to 0.7, or 0.2 to 0.6, for example 0.5.

[0046] The synthetic mixture may optionally contain at least one source of halide ions (W) different from fluoride ions, which may be selected from the group consisting of chlorides, bromides, or iodides. The source of halide ions (W) may be any compound capable of releasing halide ions in the molecular sieve synthetic mixture. For example, the halide ion may be present as a counterion of a structure directing agent (Q). Non-limiting examples of halide ion sources include hydrogen chloride, ammonium chloride, hydrogen bromide, ammonium bromide, hydrogen iodide, and ammonium iodide; salts containing one or more halide ions, such as metal halides, preferably the metal being an alkali metal or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium, or barium; or tetraalkylammonium halides, such as tetramethylammonium halide or tetraethylammonium halide. In addition, small amounts of halide ions (W) may be present as impurities, for example, in any source of alkali metal or alkaline earth metal cations (M). Halide ions (W) may be present even when the W / Y molar ratio is 0 to 0.2, for example 0 to 0.1, for example less than 0.1, or even 0. In another embodiment, the synthetic mixture may not contain substantially any halide ions (W).

[0047] Optionally, the synthetic mixture may contain at least one hydroxide ion (OH) source. For example, hydroxide ions can be present by using aluminum hydroxide or sodium aluminate as a counterion for the structure directing agent (Q) or as an Al source. Suitable hydroxide ion sources can also be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide and mixtures thereof, e.g., 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, and most often sodium hydroxide and / or potassium hydroxide. The synthetic mixture may contain hydroxide ion sources in an OH / Y molar ratio of 0 to 1.0, e.g., 0.01 to 0.8 or 0.1 to 0.7, e.g., 0.5. In another embodiment, the synthetic mixture may not contain substantially any hydroxide ions (OH).

[0048] If the synthetic mixture consists of a hydroxide ion source, the fluoride ion source neutralizes the hydroxide ions at least partially. In a preferred embodiment, the relative amounts of fluoride ions and hydroxide ions can be adjusted so that the pH of the synthetic mixture is less than 10, particularly at most 9, e.g., about 7, 8, or 9. For example, the pH of the synthetic mixture is about 7 when the fluoride ion source is HF, and about 8-9 when the fluoride ion source is NH4F. There is no particular lower limit to the pH of the synthetic mixture. Typically, the pH of the synthetic mixture is at least 3, e.g., at least 4, e.g., at least 5 or 6. In the context of this disclosure, the pH of the synthetic mixture is determined to an accuracy of ±0.05 by measuring with a pH meter at 20°C, in accordance with IUPAC Recommendation 2002 (RP Buck et al., 2002, Pure Appl. Chem., v. 74(11), pp. 2169-2200). A commercially available pH meter suitable for pH measurement is the Mettler Toledo FE20 pH meter. pH calibration was performed using a three-point calibration with standard buffer solutions at pH=4.0, pH=7.0, and pH=10.00. The resolution is as follows: 0.01 pH; 1 mV; and 0.1 °C. The error limits are as follows: 0.01 pH; ±1 mV; and ±0.5 °C.

[0049] Optionally, the synthetic mixture may contain one or more sources of alkali or alkaline earth metal cations (M). If present, M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, calcium, magnesium, strontium, barium, and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. If present, the sodium source may be sodium hydroxide, sodium aluminate, sodium silicate, or sodium salts such as NaCl, NaBr, or sodium nitrate. If present, the potassium source may be potassium hydroxide, potassium aluminate, potassium silicate, or potassium salts such as KCl, KBr, or potassium nitrate. If present, the lithium source may be lithium hydroxide, or lithium salts such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. If present, the rubidium source may be rubidium hydroxide, or rubidium salts such as RbCl, RbBr, RbI, or rubidium nitrate. If present, the calcium source may be calcium hydroxide. The magnesium source, if present, may be magnesium hydroxide. The strontium source, if present, may be strontium hydroxide. The barium source, if present, may be barium hydroxide. Furthermore, the alkali or alkaline earth metal cation (M) may be present in a source of one or more tetravalent elements X, such as one or more alumina or boron oxides and / or potassium silicate and / or sodium silicate, for example, sodium aluminate, sodium tetraborate, potassium tetraborate. The alkali or alkaline earth metal cation (M) source is advantageously soluble in water. The synthetic mixture may contain the alkali or alkaline earth metal cation (M) source in an M / Si molar ratio of 0 to 1.0, for example, 0.01 to 0.5, for example, 0.01 to 0.2 or 0.15, for example, 0 or 0.01 to 0.1 or even less than 0.1. In another embodiment, the synthetic mixture may not contain substantially any alkali or alkaline earth metal cation (M).

[0050] The synthesis may be carried out with or without the addition of nucleating seeds. When nucleating seeds are added to the synthesis mixture, the seeds may be of the same or different skeletal type as the molecular sieve obtained by this method, for example, the molecular sieve EMM-75 obtained by the above synthesis, and may be present in an appropriate amount of 0.01 to 10,000 ppm based on the synthesis mixture, for example, by weight relative to 100 to 5,000 ppm of the synthesis mixture.

[0051] The synthetic mixture typically contains water in an H2O / Y molar ratio of 1 to 50, e.g., 5 to 40 or 5 to 30, e.g., 5 or 10 to 15. Depending on the properties of the components of the base mixture, the amount of solvent in the base mixture (e.g., water from a hydroxide solution, and optionally methanol and ethanol from hydrolysis of a silica source) may be removed so that the desired molar ratio of solvent to Y molar ratio is achieved in the synthetic mixture. Preferred methods for reducing the solvent content may include evaporation under ambient air, dry nitrogen, or under a stream of dry air, or spray drying or freeze-drying. Also, if too much water is removed during the solvent removal process, water may be added to the resulting mixture to achieve the desired H2O / Y molar ratio. In some examples, if the preparation has a sufficient H2O / Y molar ratio, water removal is not necessary.

[0052] Carbon in the form of CH2 may be present in various sources of components used in the preparation of the molecular sieves of this disclosure, such as a tetravalent element source (silica source) or a trivalent element source (alumina source), and may be incorporated as bridging atoms into the resulting molecular sieve framework. Nitrogen atoms may be incorporated as bridging atoms into the framework of the molecular sieve material after the SDA has been removed.

[0053] In one or more embodiments, the synthetic mixture after solvent preparation (e.g., when the desired ratio of water to silica is achieved) may be mixed by mechanical means such as stirring or high-shear blending, and suitable homogenization of the base mixture may be ensured using a double asymmetric centrifugal mixer (e.g., FlackTek speedmixer) having a mixing speed of, for example, 1000 to 3000 rpm (e.g., 2000 rpm).

[0054] The synthetic mixture is then subjected to crystallization conditions suitable for the formation of molecular sieve material. Crystallization of the molecular sieve material may be carried out under static or stirred conditions in a suitable reactor, for example, in a Teflon®-lined or stainless steel autoclave placed in a convection oven maintained at a suitable temperature.

[0055] The crystallization in step (b) of the method described above is typically carried out at a temperature of 100–200°C, for example 120–180°C, or for example 120–150°C, for a sufficient time for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be shortened. For example, the crystallization conditions in step (b) of the method may include heating for a period of 1 to 100 days, for example 1 to 50 days, for example 1 to 30 days, for example at least 1 day or at least 5 days, and up to a maximum of 40 or 30 days. The crystallization time can be established by methods known in the art, for example, by sampling the synthetic mixture at various times and measuring the yield and X-ray crystallinity of the precipitated solid. Unless otherwise specified herein, the measurement temperature is the temperature of the ambient environment surrounding the substance being heated, for example, the temperature of the atmosphere in which the material is heated.

[0056] Typically, molecular sieves are formed in solution and can be recovered by standard means such as centrifugation or filtration. Separated molecular sieves can be washed, recovered by centrifugation or filtration, and then dried.

[0057] When the molecular sieves of this disclosure are used as adsorbents or catalysts in organic compound conversion processes, they may be at least partially dehydrated (e.g., dried). This may be done by heating them to a temperature in the range of 80 to 500°C, for example, 90 to 370°C, in an atmosphere such as air or nitrogen, and for 30 minutes to 48 hours at atmospheric pressure, a pressure lower than atmospheric pressure, or a pressure higher than atmospheric pressure. Alternatively, dehydration may be carried out at room temperature by simply placing the molecular sieves in a vacuum, although a longer time is required to obtain a sufficient amount of dehydration.

[0058] As a result of the crystallization process, the recovered product contains at least a portion of the structure-directing agent used in the synthesis within its pores. The as-synthesized molecular sieve recovered from step (c) may be subjected to heat treatment or other treatment to remove some or all of the SDA incorporated into its pores during synthesis. Heat treatment (e.g., calcination) of the as-synthesized molecular sieve typically involves exposing the material to a sufficiently high temperature and removing some or all of the SDA in an atmosphere selected from air, nitrogen, ozone, and mixtures thereof in the furnace. Pressures lower than atmospheric pressure may be used in the heat treatment, but atmospheric pressure is preferred for convenience. The heat treatment may be carried out at temperatures up to 925°C, for example, 300-700°C or 400-600°C. The measured temperature is the ambient temperature of the sample. The heat treatment (e.g., calcination) may be carried out in a box furnace in air, attached to a drying tube containing a desiccant that removes water from dry air. Heating is typically carried out for at least one minute, generally less than one day, or at most several days. Heating may be initially performed under a nitrogen atmosphere, after which the atmosphere may be switched to air and / or ozone.

[0059] Furthermore, the molecular sieves may be subjected to ion exchange treatment, for example, using aqueous ammonium salts such as ammonium nitrate, ammonium chloride, and ammonium acetate, to remove any residual alkali metal cations and / or alkaline earth metal cations present in the synthetic mixture, replacing them with protons, thereby producing the acidic form of the molecular sieves. To a desired extent, the original cations of the as-synthesized material, such as alkali metal cations, can be replaced by other cations through ion exchange. Preferred substitution cations may include hydrogen ions, hydrogen precursors (e.g., ammonium ions), and mixtures thereof. The ion exchange step may be performed after the as-produced molecular sieves have dried. The ion exchange step may be performed before or after the calcination step.

[0060] Furthermore, molecular sieves may be subjected to other treatments, such as steam treatment and / or washing with a solvent. Such treatments are well known to those skilled in the art and are performed to modify the properties of the molecular sieves to desired properties.

[0061] The molecular sieves of this disclosure may be used as adsorbents, catalysts, or catalyst supports in a wide variety of hydrocarbon conversions, such as the conversion of organic compounds to conversion products, after some or all of the SDA has been removed. Accordingly, in a fourth aspect, this disclosure relates to a process for converting an organic compound to a conversion product, the process comprising contacting the organic compound with a molecular sieve prepared according to a molecular sieve according to a first or second aspect of this disclosure, or a molecular sieve prepared according to a process according to a third aspect of this disclosure.

[0062] The molecular sieve material of this disclosure (with some or all of the SDA removed) may be used as an adsorbent, for example, to separate at least one component from a mixture of gaseous or liquid phase components with different adsorption (or sorption) properties to a material. Thus, at least one component can be partially or substantially completely separated from a mixture of components with different adsorption properties to a molecular sieve by contacting the mixture with this molecular sieve that selectively adsorbs (or sorbs) one component. For example, in a process to selectively separate one or more desired components of a feedstock from the remaining components of the feedstock, the feedstock can be contacted with an adsorbent (or sorbent) consisting of the molecular sieve of this disclosure under effective adsorption (or sorption) conditions, thereby forming an adsorption (or sorption) product and an effluent product. The one or more desired components are recovered from either the adsorption product or the effluent product.

[0063] The molecular sieves of this disclosure (in a form with some or all of the SDA removed) can also be used as catalysts for catalyzing a wide variety of organic compound transformation processes. Examples of chemical transformation processes effectively catalyzed by the molecular sieves described herein include those requiring an acid-active catalyst, either alone or in combination with one or more other catalytic agents, including other crystalline catalysts. Examples of organic transformation processes effectively catalyzed by the molecular sieves described herein include cracking, hydrocracking, isomerization, polymerization, modification, hydrogenation, dehydrogenation, dewaxing, hydrodecaying, adsorption, alkylation, rearrangement alkylation, dealkylation, hydrodecylation, disproportionation, oligomerization, dehydrogenation cyclization, methanol to olefin conversion, and denitrification (deNOx). x ) Applications and combinations thereof. The conversion of hydrocarbon raw materials can be carried out in any convenient manner, such as a fluidized bed, moving bed, or fixed bed reactor, depending on the type of process desired.

[0064] The molecular sieves of this disclosure can be incorporated into product compositions by combining them with other materials, such as binders and / or matrix materials, which impart further hardness to the final product. These other materials may be inert or catalytically active materials.

[0065] For example, it may be desirable to combine the molecular sieves of this disclosure with another material that is resistant to the temperature or other conditions used during operation. Such materials include synthetic or naturally occurring zeolites, and inorganic materials such as clay, silica and / or metal oxides, such as alumina and mixtures thereof. The metal oxides may be naturally occurring or in the form of gel-like precipitates or gels containing mixtures of silica and metal oxides. Using a resistant material with the molecular sieves of this disclosure, i.e., combining it with the molecular sieves, or having its crystals present in the synthesis of the as-produced, active molecular sieves, tends to alter the catalyst conversion and / or selectivity in certain organic conversion processes. The inert resistant material preferably functions as a diluent to control the amount of conversion in a given process, and the product 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 into naturally occurring clays, such as bentonite or kaolin, to improve the fracturing strength of the product under commercial operating conditions. These inert-resistant materials, such as clay and oxides, function as binders for the catalyst. In commercial use, it is desirable to prevent the catalyst from decomposing into powdery material, so catalysts with high pulverization strength can be beneficial.

[0066] The usable natural clays include the montmorillonite and kaolin families, which include subbentonite and kaolin known as Dixie, McNamee, Georgia, and Florida clays, or others whose main mineral component is halloysite, kaolinite, diccite, nacrite, or anauxite. Such clays can be used in their original, raw state or after firing, acid treatment, or chemical modification. Binders useful for compounding with the molecular sieves of this disclosure include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallium oxide, zinc oxide, and mixtures thereof.

[0067] In addition to the materials described above, the molecular sieves of this disclosure can be compounded with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, and silica-titania, as well as ternary compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0068] These binder materials are resistant to temperature and other conditions, such as mechanical wear that occurs in various hydrocarbon separation processes. Therefore, the molecular sieves of this disclosure may be used in the form of extruded products having a binder. They are typically bound together by forming tablets, spheres, or extruded products. Extruded products are usually formed by extruding the molecular sieves, drying them, and then calcining the resulting extruded products, optionally in the presence of a binder. Further treatments, such as steaming and / or ion exchange, may be performed as needed. Molecular sieves are optionally bound to at least 100 m 2 / g, for example, at least 200m 2 / g, optionally at least 300m 2 It may be bonded with a binder having a surface area of ​​ / g.

[0069] The relative ratio of molecular sieves to inorganic oxide matrix can vary considerably, with molecular sieve content ranging from approximately 1% to approximately 100% by weight, and more generally, particularly when the composite is prepared in the form of an extruded product, it ranges from approximately 2% to approximately 95% by weight, and optionally from approximately 20% to approximately 90% by weight.

[0070] Furthermore, the molecular sieves of this disclosure may be used in close combination with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or precious metals such as platinum or palladium, if hydrogenation-dehydrogenation functionality is required. Such hydrogenation components may be incorporated into the composition by one or more of the following processes: co-crystallization; replacement of the composition with elements such as Group IIIA elements, such as aluminum, to the extent that they are present in the structure; or physically close mixing thereof. Such components can also be impregnated into the interior or surface of the molecular sieve, for example, by treating the molecular sieve with metal hydride-containing ions. For example, in the case of platinum, suitable platinum compounds for this purpose include a variety of compounds containing chloroplatinic acid, platinum chloride, and platinumamine complexes. Combinations of metals and methods for introducing them can also be used.

[0071] Those skilled in the art will understand that molecular sieves obtained by the methods disclosed herein may contain impurities, such as amorphous materials, unit cells having different topologies (e.g., quartz or molecular sieves of different skeleton types or different layered phases, which may or may not affect the performance of the resulting catalyst), and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). Typical examples of molecular sieves of different skeleton types that may be present with the molecular sieves of this disclosure include, for example, IWV skeleton type molecular sieves, such as ITQ-27. The molecular sieves of this disclosure are preferably substantially free of impurities. As used herein, the term “substantially free of impurities” (or alternatively “substantially pure”) includes small amounts (less than 50 wt%), preferably less than 20 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%, and most preferably less than 1 wt% (e.g., less than 0.5 wt% or 0.1 wt%) of such impurities (or “non-EMM-75” skeletal material), where the wt% value is based on the combined weight of the impurities and the pure molecular sieve. The amount of impurities can be appropriately identified by powder XRD, rotational electron diffraction, and / or SEM / TEM (e.g., various crystal morphological methods).

[0072] The molecular sieves described herein are substantially crystalline. As used herein, the term “crystalline” refers to the crystalline solid form of a material and includes, but is not limited to, single-component or multi-component crystalline forms (e.g., solvates, hydrates, and cocrystals). Crystallinity means having a regular repeating and / or ordered arrangement of molecules and possessing a recognizable crystalline lattice. For example, molecular sieves may have varying water or solvent content. Various crystalline lattices can be identified by solid-state characterization methods such as XRD (e.g., powder XRD). Other characterization methods known to those skilled in the art may further help in identifying the crystalline form, as well as in determining stability and solvent / water content. As used herein, the term “substantially crystalline” means that the majority (greater than 50 wt%) of the weight of the material sample described is crystalline, and the remainder of the sample is amorphous. In one or more embodiments, a substantially crystalline sample has a degree of crystallinity of at least 95% (e.g., 5% amorphous form), at least 96% (e.g., 4% amorphous form), at least 97% (e.g., 3% amorphous form), at least 98% (e.g., 2% amorphous form), at least 99% (e.g., 1% amorphous form), and 100% (e.g., 0% amorphous form).

[0073] Aspects of this disclosure will be described in more detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit this disclosure in any way. Those skilled in the art will readily recognize that various parameters can be changed or modified to obtain essentially the same results. [Examples]

[0074] The present invention will be further described below without limiting its scope.

[0075] In these examples, X-ray diffraction (XRD) patterns of as-synthesized and calcined materials were recorded in continuous mode using an X-ray powder diffraction system (Bruker DaVinci D8 Discovery instrument) in a Bragg-Bentano configuration with a Vantec500 detector in the CuKα range of 4–36 degrees 2θ. The frame spacing and interval d were calculated in angstroms, and the relative intensity I / I0 of a line is the ratio of the peak intensity to the ratio of the peak intensity of the strongest line. Intensities are uncorrected for Lorentz and polarization effects. The position of the diffraction peaks at 2θ, and the relative peak area intensity of the line, I / I0 (where I0 is the intensity of the strongest line above the background), were determined using the MDI Jade peak search algorithm. It should be understood that diffraction data described as a single line may consist of multiple overlapping lines, which may appear as decomposed or partially decomposed lines under certain conditions, such as differences in crystallographic changes. Typically, crystallographic changes can include small changes in unit cell parameters and / or changes in crystal symmetry, without changes in skeletal bonding. These small effects include changes in relative intensity and can also result from differences in cation content, skeletal composition, and pore filling properties and degree, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0076] Scanning electron microscope (SEM) images of the as-synthesized material were obtained using a Hitachi 4800 scanning electron microscope. The SEM images were used to assess the purity of the product. The presence of distinctly different crystalline morphologies in the SEM images may indicate impurities in the form of other crystalline materials. Such approximate analysis can be particularly useful in identifying the presence of relatively small amounts of crystalline impurities that may not be detectable by the XRD pattern of the product.

[0077] The total BET surface area of ​​the material (S BETThe external surface area (S) of the material was measured using the BET method, described in S. Brunauer, PH. Emmett et al., J. Am. Chem. Soc., 1938, v.60, pg.309, using nitrogen adsorption-desorption at liquid nitrogen temperature. The contents of this document are incorporated herein by reference. ext The surface area (S) of the micropores of the material was obtained by the t-plot method. micro ) is the total BET surface area (S BET ) from the external surface area (S ext It was calculated by subtracting ).

[0078] Micropore volume (V) of the material micro ) and total pore volume (V tot These can be determined using methods known in the relevant technical field. For example, the micropore and total pore volumes of a material can be measured using physicoadsorption of nitrogen, and the data can be analyzed by the t-plot method, which is described by Lippens, BC et al., "Studies on pore system in catalysts: V. The t method," J. Catal., v.4, pg.319, 1965, which describes the micropore and total pore volume method and is incorporated herein by reference.

[0079] Examples 2 to 6, as well as the molar ratios and conditions used in the synthesis of the obtained products, are described in detail below and summarized in Table 3.

[0080] Example 1: Synthesis of 2-ethyl-1,3-dimethylbenzimidazolium hydroxide A mixture of 15 g of 2-ethyl-benzimidazole, 21 g of potassium carbonate (K2CO3), and 58.3 g of iodomethane in 170 mL of acetonitrile (CH3CN) was heated overnight at 60°C. The reaction mixture was cooled to room temperature, the potassium carbonate was filtered from the solution, and the acetonitrile in the filtrate was removed using a rotary evaporator. Chloroform was added to the flask to precipitate the residual potassium salt, and the solution was then filtered again. The filtrate in chloroform yielded pure 2-ethyl-1,3-dimethyl-1H-benzo[d]imidazole-3-ium iodide.

[0081] The iodide salt of 2-ethyl-1,5-dimethylbenzimidazolium was then ion-exchanged to its hydroxide form using the ion-exchange resin Amberlite® IRN78 OH in a weight ratio of 1:3.5:5 iodide:resin:water. The exchange was carried out overnight at room temperature.

[0082] Example 2: Synthesis of EMM-75 with a Si / Al molar ratio of approximately 15 using TEOS and Al(OH)3 A mixture of 1.2 g of tetraethyl orthosilicate (TEOS, >99 wt%) and 0.035 g of Al(OH)3 (Al(OH)3, Sigma, 54 wt% Al2O3) was hydrolyzed at room temperature for approximately 2-3 hours in 13.5 mL of 2-ethyl-1,3-dimethylbenzimidazolium hydroxide (QOH) solution (4 wt%), and 0.12 mL of HF (48 wt% solution) was added to the mixture. This gel was left at room temperature for several days, and ethanol and water were removed to produce a synthetic mixture with the following molar ratio composition. 10H2O:1SiO2:0.033Al2O3:0.5QOH:0.5HF

[0083] This thick paste was homogenized by hand in a PTFE container and transferred to a 23 mL PTFE-lined stainless steel Parr autoclave. The autoclave was maintained at 135°C for 28 days while rotating in a convection oven (approximately 40 ppm). The product was separated by filtration, rinsed with deionized water, and dried at 90°C in a ventilated drying oven. The as-synthesized material was then calcined at 580°C in air in a box furnace with a heating rate of 3°C / min. The temperature was maintained at 580°C for 8 hours, after which the box furnace was cooled.

[0084] XRD analysis of the as-synthesized and calcined products showed a unique powder XRD pattern that did not match any known molecular sieves or zeolites, indicating the pure as-synthesized and calcined EMM-75 products. Figure 2 shows an SEM image of the as-synthesized material. Figures 1 and 2 show the powder XRD patterns of the as-synthesized and calcined EMM-75 materials of Example 2. Tables 4 and 5 below list the peaks and intensities of the as-synthesized and calcined EMM-75 materials of Example 2. Figure 3 shows an SEM image of the as-synthesized product of Example 2.

[0085] The EMM-75 material in its as-manufactured state exhibited a layered phase with monoclinic symmetry (a: 7.3000 (15) Å; b: 17.7000 (40) Å; c: 25.0000 (50) Å; β: 95.000 (30)°) and contained approximately 17% silanol defects. However, upon sintering, it transformed into orthorhombic cells with increased symmetry (a: 7.5900 (15) Å; b: 17.8700 (40) Å; c: 22.3500 (50) Å), and the defects were healed. The sintered EMM-75 material has 48 Si atoms in a single unit cell. The calcined EMM-75 material has a structure similar to MOR zeolite, with one 12-membered ring being more elliptical (6.5 Å × 8.3 Å in EMM-75 compared to 6.5 Å × 7 Å in MOR), and the 8-membered ring being narrower (5.7 Å × 2.3 Å in EMM-75 compared to 5.7 Å × 2.6 Å in MOR). Figure 4 shows the structure of the EMM-75 material along the

[0100] direction.

[0086] The surface area of ​​the micropores of the EMM-75 material used in the firing process in Example 2 (S micro ) is 174m 2 / g, and its external surface area (S ext ) is 45m 2 / g is the total pore volume (V tot ) is 0.23cm 3 / g, micropore volume (V micro ) is 0.074 cm 3 It was / g.

[0087] Example 3: Synthesis of EMM-75 with a Si / Al molar ratio of approximately 12.5 using TEOS and Al(OH)3 This example was carried out under the same conditions as in Example 2, but the Si / Al ratio was reduced to 12.5, resulting in a synthetic mixture with the following molar ratio composition. 10H2O:1SiO2:0.04Al2O3:0.5QOH:0.5HF

[0088] After heating at 135°C for 28 days, a pure EMM-75 product was obtained, and its XRD pattern was identified.

[0089] Example 4: Synthesis of EMM-75 with a Si / Al molar ratio of approximately 15 using TEOS and Al(OiPr)3 This example was carried out under the same conditions as in Example 2, with the following composition in terms of molar ratio: 10H2O:1SiO2:0.033Al2O3:0.5QOH:0.5HF The compound was found to have the following properties, however, aluminum isopropoxide (Al(OiPr)3, 98 wt%, Sigma) was used as the Al source. After heating at 135°C for 28 days, a pure EMM-75 product was obtained, and its XRD pattern was identified (Figure 5). Figure 6 shows an SEM image of the as-synthesized product from Example 3.

[0090] The surface area of ​​the micropores of the EMM-75 material used in the firing process of Example 3 (S micro ) is 155m 2 / g, and its external surface area (S ext) is 147m 2 / g is the total pore volume (V tot ) is 0.73cm 3 / g, micropore volume (V micro ) is 0.069cm 3 It was / g.

[0091] Example 5: Synthesis of EMM-75 with a Si / Al molar ratio of approximately 20 using TEOS and Al(OiPr)3 This example was carried out under the same conditions as in Example 4, but the Si / Al ratio was increased to 20, resulting in a synthetic mixture with the following composition in terms of molar ratio. 10H2O:1SiO2:0.025Al2O3:0.5QOH:0.5HF

[0092] After heating at 135°C for 28 days, a pure EMM-75 product was obtained, and its XRD pattern was identified.

[0093] Example 6: Synthesis of EMM-75 with a Si / Al molar ratio of approximately 40 using TEOS and Al(OiPr)3 This example was carried out under the same conditions as in Example 4, but the Si / Al ratio was increased to 20, resulting in a synthetic mixture with the following composition in terms of molar ratio. 10H2O:1SiO2:0.0125Al2O3:0.5QOH:0.5HF

[0094] After heating at 135°C for 28 days, the XRD pattern showed that the EMM-75 product was obtained from a different layered phase impurity. [Table 7] [Table 8] [Table 9]

[0095] While the present invention has been described and explained with reference to specific embodiments, those skilled in the art will understand that the invention is suitable for many different changes, modifications, and variations not specifically described herein. Furthermore, where numerical lower and upper limits are described herein, it will be obvious to those skilled in the art that a range exists between either the lower or upper limit. Also, all numerical values ​​in the detailed descriptions herein are modified to be "approximately" given, and experimental errors and variations assumed by those skilled in the art should be taken into consideration.

[0096] Where any integer or element for which a known, obvious, or foreseeable equivalent is referred in the foregoing description, such equivalents are subsequently incorporated herein as if they were individually described. Claims should be consulted to determine the true scope of the invention, and the true scope should be understood to encompass any of such equivalents. Furthermore, the reader should understand that inventive features or integers such as “preferred,” “advantageous,” or “convenient” are optional and do not limit the scope of an independent claim. Moreover, such optional integers or features may be beneficial in some embodiments of the invention, while being undesirable in other embodiments, and therefore may be absent.

[0097] In addition or alternatively, the present invention relates to the following embodiments:

[0098] Embodiment 1: A molecular sieve having an X-ray diffraction pattern that includes at least 14 peaks in Table 1 in the firing configuration.

[0099] Embodiment 2: A molecular sieve according to Embodiment 1, wherein the calcined form has an X-ray diffraction pattern that includes at least 15, preferably at least 16, more preferably at least 17, and most preferably all, peaks selected from Table 1.

[0100] Embodiment 3: A molecular sieve according to Embodiment 1 or 2, wherein formula II: (m)X2O3:YO2 (Formula II) [Where, 0.01 ≦ m ≦ 0.1, X is a trivalent element, and Y is a tetravalent element.] A molecular sieve having the molecular formula of

[0101] Embodiment 4: The molecular sieve according to Embodiment 3, wherein X contains aluminum and / or boron, or is aluminum and / or boron, preferably, X contains aluminum, or is aluminum, the molecular sieve.

[0102] Embodiment 5: The molecular sieve according to Embodiment 3 or 4, wherein Y contains silicon and / or germanium, or is silicon and / or germanium, preferably contains silicon, or is silicon, the molecular sieve.

[0103] Embodiment 6: A molecular sieve having an X-ray diffraction pattern that contains at least 9 peaks in Table 2 in its as-synthesized form.

[0104] Embodiment 7: The molecular sieve according to Embodiment 6, having an X-ray diffraction pattern that contains at least 10, preferably at least 11, more preferably at least 12, and most preferably all the peaks selected from Table 2 in its as-synthesized form.

[0105] Embodiment 8: The molecular sieve according to Embodiment 6 or 7, wherein Formula III: (q)Q:(m)X2O3:YO2 (Formula III) [Where, 0 < q ≦ 0.7, 0.01 ≦ m ≦ 0.1, X is a trivalent element, Y is a tetravalent element, Q is Formula I:

Chemical formula

[0106] Embodiment 9: A molecular sieve according to Embodiment 8, wherein X contains aluminum and / or boron, or is aluminum and / or boron, preferably X contains aluminum or is aluminum.

[0107] Embodiment 10: A molecular sieve according to Embodiment 8 or 9, wherein Y contains silicon and / or germanium, or is silicon and / or germanium, preferably containing silicon, or is silicon.

[0108] Embodiment 11: A molecular sieve according to any one of Embodiments 1 to 10, wherein at least a portion of the molecular sieve crystal has a plate-like form.

[0109] Embodiment 12: A molecular sieve according to any one of Embodiments 1 to 11, wherein the aluminosilicate is an aluminosilicate or borosilicate, preferably an aluminosilicate having a Si / Al molar ratio of 5:50.

[0110] Embodiment 13: A method for manufacturing a molecular sieve according to any one of Embodiments 1 to 12, (a) Water, a source of oxides of a tetravalent element (Y), a source of oxides of a trivalent element (X), Formula I: [ka] A step of preparing a synthetic mixture comprising a structure-directing agent (Q) comprising a 2-ethyl-1,3-dimethylbenzimidazolium cation, a fluoride ion source (F), and optionally a hydroxide ion source (OH), (b) A step of heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve, (c) A step of recovering at least a portion of the molecular sieve from step (b), (d) A method comprising the step of optionally processing the molecular sieve recovered in step (c) to remove at least a portion of the structural directing agent (Q).

[0111] Embodiment 14: The method according to Embodiment 13, wherein the structure directing agent (Q) is a halide, hydroxide, or nitrate, preferably in the form of a hydroxide.

[0112] Embodiment 15: A method according to Embodiment 13 or Embodiment 14, wherein the tetravalent element (Y) comprises silicon and / or germanium, preferably the tetravalent element (Y) is silicon and / or germanium, and more preferably the tetravalent element (Y) is silicon.

[0113] Embodiment 16: A method according to any one of Embodiments 13 to 15, wherein the trivalent element (X) comprises aluminum and / or boron, more preferably, the trivalent element (X) is aluminum and / or boron, particularly aluminum.

[0114] Embodiment 17: The synthetic mixture has the following composition in molar ratio units: [Table 10] The method according to any one of embodiments 13 to 16, having the following characteristics.

[0115] Embodiment 18: A method according to any one of Embodiments 13 to 17, wherein the synthetic mixture is substantially free of alkali or alkaline earth metal cations (M), or, if any alkali or alkaline earth metal cations (M) are present, the molar ratio M / Y is at most 1.0, preferably at most 0.5, particularly at most 0.2, and more specifically less than 0.1.

[0116] Embodiment 19: The method according to any one of Embodiments 13 to 18, wherein the synthetic mixture has a pH of less than 10, preferably up to 9.

[0117] Embodiment 20: The method according to any one of Embodiments 13 to 19, wherein the synthetic mixture has a pH of at least 3, preferably at least 4.

[0118] Embodiment 21: A process for converting an organic compound into a conversion product, comprising contacting the organic compound with a molecular sieve described in any one of Embodiments 1 to 12.

Claims

1. In terms of firing method, Table 1: Table 1 A molecular sieve having an X-ray diffraction pattern containing at least 14 peaks.

2. A molecular sieve according to claim 1, wherein, in its firing form, it has an X-ray diffraction pattern that includes at least 15, preferably at least 16, more preferably at least 17, and most preferably all, peaks selected from Table 1.

3. A molecular sieve according to claim 1 or 2, wherein formula II: (m)X ２ O ３ : YO ２ (Formula II) [In the formula, 0.01 ≤ m ≤ 0.1, X is a trivalent element, Y is a tetravalent element, In particular, X contains aluminum and / or boron, or is aluminum and / or boron, preferably X contains aluminum, or is aluminum. Y contains silicon and / or germanium, or is silicon and / or germanium, preferably containing silicon or being silicon. Molecular sieves having the molecular formula.

4. In its synthesized form, see Table 2: Table 2 A molecular sieve having an X-ray diffraction pattern containing at least nine peaks.

5. A molecular sieve according to claim 4, wherein in its as-synthesized form, the molecular sieve has an X-ray diffraction pattern comprising at least 10, preferably at least 11, more preferably at least 12, and most preferably all, peaks selected from Table 2.

6. A molecular sieve according to claim 4 or 5, wherein formula III: (q) Q: (m) X ２ O ３ : YO ２ (Formula III) [In the formula, 0 < q ≤ 0.7, 0.01 ≤ m ≤ 0.1, X is a trivalent element, Y is a tetravalent element, Q is given by equation I: 【Chemistry 1】 It contains the 2-ethyl-1,3-dimethylbenzimidazolium cation, In particular, X contains aluminum and / or boron, or is aluminum and / or boron, preferably X contains aluminum, or is aluminum. Y contains silicon and / or germanium, or is silicon and / or germanium, preferably containing silicon or being silicon. Molecular sieves having the molecular formula.

7. A molecular sieve according to any one of claims 1 to 6, wherein at least a portion of the molecular sieve crystal has a plate-like form.

8. A molecular sieve according to any one of claims 1 to 7, wherein the molecular sieve is an aluminosilicate or borosilicate, preferably an aluminosilicate having a Si / Al molar ratio of 5:

50.

9. A method for producing a molecular sieve according to any one of claims 1 to 8, (a) Water, a source of oxides of a tetravalent element (Y), a source of oxides of a trivalent element (X), formula I: 【Chemistry 2】 A step of preparing a synthetic mixture comprising a structure-directing agent (Q) comprising a 2-ethyl-1,3-dimethylbenzimidazolium cation, a fluoride ion source (F), and optionally a hydroxide ion source (OH), (b) A step of heating the synthetic mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve, (c) A step of recovering at least a portion of the molecular sieve from step (b), (d) A step of optionally processing the molecular sieves recovered in step (c) to remove at least a portion of the structural directing agent (Q), A method that includes this.

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

11. The method according to claim 9 or 10, The tetravalent element (Y) includes silicon and / or germanium, preferably the tetravalent element (Y) is silicon and / or germanium, and more preferably the tetravalent element (Y) is silicon. A method wherein the trivalent element (X) comprises aluminum and / or boron, more preferably, the trivalent element (X) is aluminum and / or boron, and particularly aluminum.

12. The synthetic mixture has the following composition in terms of molar ratio: Table 3 The method according to any one of claims 9 to 11, comprising:

13. A method according to any one of claims 9 to 12, The synthetic mixture is substantially free of alkali or alkaline earth metal cations (M), or A method in which, if any alkali or alkaline earth metal cation (M) is present, the molar ratio M / Y is at most 1.0, preferably at most 0.5, particularly at most 0.2, and more specifically less than 0.

1.

14. The method according to any one of claims 9 to 13, wherein the synthetic mixture has a pH of less than 10, preferably up to 9.

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

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