EMM-75 molecular sieve compositions, synthesis and uses

Abstract

Molecular sieves referred to as EMM-75 and characterized by unique powder XRD profiles, methods for their preparation and their uses.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 492,292, filed on March 27, 2023, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to molecular sieve compositions, methods for preparing the same, and uses thereof. Background of the Invention

[0005] Natural and synthetic molecular sieve materials can be used as adsorbents and have catalytic properties to hydrocarbon conversion reactions. Some molecular sieves, such as zeolites, AlPO and mesoporous materials, are ordered porous crystalline materials with a clear and definite crystal structure determined by X-ray diffraction (XRD). Some molecular sieves are ordered and produce specific identifiable XRD patterns. In some molecular sieve materials, there may be a large number of cavities, which can be interconnected by several channels or holes. These cavities and holes are uniform in size in specific molecular sieve materials. Because the size of these holes is enough to allow the adsorption of molecules of a specific size, while repelling those of larger sizes, these materials have gradually been referred to as "molecular sieves" and are used to various industrial processes, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization and isomerization.

[0006] Molecular sieves used in catalysis and adsorption include any of natural or synthetic crystalline molecular sieves. These zeolites and their isotypes are classified by the International Zeolite Association Structure Commission according to the rules of the IUPAC Zeolite Nomenclature Committee. According to this classification, framework-type zeolites and other crystalline microporous molecular sieves with established structures are assigned three-letter codes and are described in "Atlas of Zeolite Framework Types", edited by Ch. Baerlocher, L.B. McCusker and D.H. Olson, Elsevier, 6th edition, 2007, which is incorporated herein by reference. These zeolites and their isotypes are also described in http: / / america.iza-structure.org / IZA-SC / ftc_table.php middle.

[0007] The idealized inorganic framework structure of a zeolite is a silicate framework in which all tetrahedral atoms are connected to their four next-nearest-neighbor tetrahedral atoms through oxygen atoms. The term "silicate" as used herein refers to a substance containing at least silicon and oxygen atoms (i.e., -O-Si-O-Si-) alternately bonded to each other and optionally including other atoms within the inorganic framework structure, such as atoms of boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc). The atoms other than silicon and oxygen in the framework silicate occupy a portion of the lattice sites that would otherwise be occupied by silicon atoms in an 'all-silicon' framework silicate. Therefore, the term "framework silicate" as used herein refers to an atomic lattice comprising any one of silicates, borosilicates, gallosilicates, ferrosilicates, aluminosilicates, titanosilicates, zinc silicates, vanadosilicates, and the like.

[0008] The structure of the framework silicate within a given zeolite determines the size of the pores or channels present therein. Pore or channel size can determine the type of process for which a given zeolite is suitable. Currently, more than 200 unique zeolite framework silicate structures are known and recognized by the International Zeolite Association's Structure Committee, which defines a range of pore geometries and orientations.

[0009] The framework silicates of zeolites or molecular sieves are generally characterized by their ring size, wherein the ring size refers to the number of silicon atoms (or replacement atoms, such as those listed above) that are tetrahedrally coordinated with oxygen atoms in the ring to define pores or channels within the zeolite. For example, an "8-membered ring" zeolite refers to a zeolite having pores or channels defined by 8 alternating tetrahedral atoms and 8 oxygen atoms in the ring. The pores or channels defined within a given zeolite can be symmetrical or asymmetrical depending on the various structural constraints present in the particular framework silicate.

[0010] Zeolite can be classified as having small pores, medium pores, large pores and ultra-large pore structures according to the pore windows defined by 8, 10, 12 and more than 12 T atoms, respectively. Ultra-large pore zeolites (>12R) include, for example, AET (14R, such as ALPO-8), SFN (14R, such as SSZ-59), VFI (18R, such as VPI-5), CLO (20R, such as Cloverite) and ITV (30R, such as ITQ-37) framework type zeolites. Ultra-large pore zeolites typically have a free pore size greater than about 0.8 nm. Large pore zeolites (12R) include, for example, LTL, MAZ, FAU, EMT, OFF, *BEA, MOR and SFS framework type zeolites, such as chelite, offretite, zeolite L, zeolite Y, zeolite X, ω zeolite, ZSM-2, zeolite T, beta zeolite and SSZ-56. The pore size of zeolite is generally 0.45-0.6nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. The pore size of zeolite is generally 0.6-0.8nm. Small pore size zeolites typically have a free pore diameter of 0.3-0.45 nm.

[0011] The synthesis of molecular sieve materials typically involves hydrothermal crystallization of a synthesis mixture containing a source of all the elements present in the molecular sieve (or zeolite), such as a silica source, but also an alumina source, etc. In many cases, 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 is believed to act as a template around which certain molecular sieve structures can form, thereby promoting the formation of the desired molecular sieve. Various compounds, including various types of quaternary ammonium cations, have been used as structure directing agents. Molecular sieve (or zeolite) crystals typically form around the structure directing agent, wherein once crystallization is complete, the structure directing agent occupies the pores in the molecular sieve. Therefore, the "as-synthesized" (or "as-prepared") molecular sieve contains the structure directing agent in its pores, so that after crystallization, the "as-synthesized" molecular sieve is typically subjected to a treatment step, such as a calcination step, to remove the structure directing agent.

[0012] Although many different molecular sieves have been discovered, there is a continuing need for new molecular sieves (or zeolites) with ideal properties for gas separation and drying, organic conversion reactions, and other applications. New molecular sieves can contain new internal pore structures that provide enhanced selectivity in these processes. It is also important to discover new structure-directing agents and more efficient methods for synthesizing molecular sieves to facilitate the preparation of new molecular sieves and / or reduce the cost of preparing known molecular sieves.

[0013] Overview

[0014] The present disclosure relates to molecular sieves, methods for their preparation, and uses thereof.

[0015] The present disclosure relates in a first aspect to a molecular sieve having, in its calcined form (e.g., wherein at least a portion of the SDA has been removed), an X-ray diffraction pattern comprising at least 14, or at least 15, or at least 16, or at least 17, 2θ angle peaks, such as all of those in Table 1:

[0016] Table 1

[0017]

[0018]

[0019] The present disclosure relates in a second aspect to a molecular sieve having, in its as-synthesized form (e.g., where SDA has not been removed), an X-ray diffraction pattern comprising at least 9, or at least 10, or at least 11, or at least 12, 2θ angle peaks such as all of those in Table 2:

[0020] Table 2

[0021] 2θ angle (±0.20) Relative intensity [100×I / (Io)] 6.21 10-40 6.81 60-100 11.51 30-60 13.37 10-20 15.58 5-15 16.16 10-20 18.11 5-15 20.05 40-70 25.02 60-100 26.10 20-40 26.48 50-80 28.59 <10 31.53 5-15

[0022] The present disclosure relates in a third aspect to a method for preparing a molecular sieve, in particular a molecular sieve as defined in the first and / or second aspects of the present disclosure, comprising the following steps: (a) preparing a mixture comprising water, an oxide source of a tetravalent element (Y), an oxide source of a trivalent element (X), 2-ethyl-1,3-dimethylbenzimidazole containing formula I; A synthetic mixture of a cationic structure directing agent (Q), a source of fluoride ions (F), and optionally, a source of hydroxide ions (OH):

[0023]

[0024] (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100-200° 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 (Q).

[0025] In a fourth aspect, the present disclosure relates to a method for converting an organic compound into a conversion product, comprising contacting the organic compound with a molecular sieve prepared according to the method of the first or second aspect of the present disclosure or according to the third aspect of the present disclosure.

[0026] 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 with respect to one aspect of the present invention may be incorporated into other aspects of the present invention. In particular, any two or more of the features described in this specification, including those described in this summary, may be combined to form a combination of features not specifically described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The powder XRD pattern of the as-synthesized EMM-75 material of Example 2 is shown.

[0028] Figure 2 The powder XRD pattern of the calcined EMM-75 material of Example 2 is shown.

[0029] Figure 3 An SEM image of the as-synthesized product of Example 2 is shown.

[0030] Figure 4 Shown is the structure of EMM-75 material along the

[100] direction.

[0031] Figure 5 Shown are the powder XRD patterns of the as-synthesized and calcined EMM-75 material of Example 4.

[0032] Figure 6 An SEM image of the as-synthesized product of Example 4 is shown.

[0033] Detailed description

[0034] The present disclosure relates to a molecular sieve composition, a method for preparing the same, and uses thereof. The molecular sieve may be referred to as EMM-75 molecular sieve, EMM-75 zeolite, or EMM-75 material.

[0035] The present disclosure relates in a first aspect to a molecular sieve having, in its calcined form (e.g., wherein at least a portion of the SDA has been removed), an X-ray diffraction pattern comprising at least 14, or at least 15, or at least 16, or at least 17, 2θ angle peaks, such as all of those in Table 1:

[0036] Table 1

[0037]

[0038]

[0039] In another embodiment, the molecular sieve, in its calcined form, may have an X-ray diffraction pattern comprising at least 14, or at least 15, or at least 16, or at least 17, peaks such as all of those in Table 1A, wherein the d-spacing values ​​have deviations determined based on the corresponding deviations of ±0.20 2-theta degrees when converted to corresponding values ​​of d-spacing using Bragg's law:

[0040] Table 1A

[0041]

[0042] In yet another embodiment, the molecular sieve may have an X-ray diffraction pattern in its calcined form that includes at least 10, such as at least 11, or at least 12, or at least 14, or all of the 2θ angle peaks in Table 1 or 1A having a relative intensity of at least 10-30, for example, 10 2θ angle peaks in Table 1 or 1A having a relative intensity of at least 20-40.

[0043] The XRD patterns with the XRD peaks described herein were obtained using Cu(K α )ray.

[0044] In one or more other embodiments, the molecular sieve in its calcined form may have a 3 / g, such as 0.05-0.1cm 3 / g, for example 0.07cm 3 / g of micropore volume.

[0045] In one or more other embodiments, the molecular sieve in its calcined form may have a molecular weight of 75 to 500 m 2 / g, such as 100-300m 2 / g, for example, about 150-180m 2 / g of micropore surface area, and / or 10-300m 2 / g, such as 30-200m 2 / g, for example 45-155m 2 / g of external surface area.

[0046] In one or more other embodiments, the molecular sieve, in its calcined form, may optionally be represented by the formula II:

[0047] (m) X2O3:YO2 Formula II, wherein 0.01≤m≤0.1, X is a trivalent element and Y is a tetravalent element. Y may comprise or be Si and / or Ge, for example, Y may comprise or be Si. X may comprise or be Al and / or B, for example, X may comprise or be Al. In embodiments where Y is Si and X is Al, the molecular sieve is an aluminosilicate. In embodiments where Y is Si and X is B, the molecular sieve is a borosilicate. The oxygen atoms in Formula II may be replaced by carbon atoms (for example, in the form of CH2), which may come from the source of the components used to prepare the molecular sieve in its original form. The oxygen atoms in Formula II may also be replaced by nitrogen atoms, for example, after SDA has been removed. Formula II may represent the skeleton of a typical molecular sieve defined in the present disclosure in its calcined form and is not intended to be the sole representative of the molecular sieve. The molecular sieve may contain SDA and / or impurities in its calcined form after appropriate treatment to remove SDA and impurities, which are not considered in Formula II. Furthermore, Formula II does not include protons and charges compensating for ions that may be present in the calcined molecular sieve.

[0048] The variable m represents the molar ratio relationship of X2O3 to YO2 in Formula 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 (e.g., a Si / Al molar ratio of 20). m can vary from 0.01 to 0.1, such as at least 0.01, or at least 0.0125, preferably greater than 0.0125, or at least 0.017 to at most 0.1, or at most 0.07, or at most 0.05, such as about 0.025, 0.03, or 0.04. The molar ratio of Y to X can be from 5 to 50, such as at least 5, or at least 7.5, or at least 10, and at most 50, or at most 40, preferably at most less than 40, or at most 30, such as about 12.5, 15, or 20.

[0049] The present disclosure relates in a second aspect to a molecular sieve, in particular a molecular sieve as defined in the first aspect, which in its as-synthesized form (e.g., from which SDA has not been removed) has an X-ray diffraction pattern comprising at least 9, or at least 10, or at least 11, or at least 12 2θ angle peaks, such as all of those in Table 2:

[0050] Table 2

[0051] 2θ angle (±0.20) Relative intensity [100×I / (Io)] 6.21 10-40 6.81 60-100 11.51 30-60 13.37 10-20 15.58 5-15 16.16 10-20 18.11 5-15 20.05 40-70 25.02 60-100 26.10 20-40 26.48 50-80 28.59 <10 31.53 5-15

[0052] In another embodiment, the molecular sieve, in its as-synthesized form, may have an X-ray diffraction pattern comprising at least 9, or at least 10, or at least 11, or at least 12, peaks such as all of those in Table 2A, wherein the d-spacing values ​​have deviations determined based on the corresponding deviations of ±0.20 2θ degrees when converted to corresponding values ​​of d-spacings using Bragg's law:

[0053] Table 2A

[0054]

[0055] In yet another embodiment, the X-ray diffraction pattern of the molecular sieve, as synthesized, may include at least 6, such as at least 7, or at least 8, or all of the 2θ angle peaks having a relative intensity of at least 10-20 in Table 2 or 2A, for example 9 of the 2θ angle peaks having a relative intensity of at least 10-40 or 20-40 in Table 2 or 2A.

[0056] The XRD pattern having the XRD peaks described herein uses Cu(K α ) radiation.

[0057] In one or more other embodiments, the molecular sieve, as synthesized, may optionally be represented by the formula III:

[0058] (q)Q:(m)X2O3:YO2 Formula III,

[0059] where 0 < q ≤ 0.7, 0.01 ≤ m ≤ 0.1, X is a trivalent element as defined for formula II, Y is a tetravalent element as defined for formula II and Q contains the 2-ethyl-1,3-dimethylbenzimidazole cation:

[0060]

[0061] Formula III may represent a typical molecular sieve as synthesized as defined in the present disclosure and thus contains a framework with a structure directing agent (Q) and is not intended as the sole representation of the material. The molecular sieve, as synthesized, may contain impurities not accounted for in formula III. In addition, formula III does not include protons and charges that compensate for ions that may be present in the as-synthesized molecular sieve.

[0062] The variable m represents the molar ratio relationship of X2O3 to YO2 in formula III. The value of the variable m in formula III is the same as those described for formula II herein.

[0063] The variable q represents the molar relationship of Q to YO2 in formula III. For example, when q is 0.1, the Q / YO2 molar ratio is 0.1. The Q / YO2 molar ratio may be greater than 0 to 0.7, such as 0.1 - 0.6, for example 0.1 - 0.5.

[0064] In other embodiments, the as-synthesized molecular sieve of the second aspect of the present disclosure is a layered phase having monoclinic symmetry [e.g., unit cell dimensions and β: ~95.0°], which contains silanol defects, for example, about 17% silanol defects. In yet another embodiment, the molecular sieve of the first aspect of the present disclosure becomes more symmetrical upon calcination, having an orthorhombic unit cell [e.g., unit cell size and The calcined molecular sieve of the first aspect of the present disclosure has 48 Si atoms in a unit cell and shares a structure similar to that of MOR zeolite, which has a more elliptical 12-membered ring size (12MR: With MOR Compared to) and the narrower 8-membered ring size (8MR: With MOR compared to).

[0065] In yet another embodiment, at least a portion of the molecular sieve crystals of the present disclosure (whether in the form of synthetic original or calcined) can have a plate-like morphology, especially a thin plate-like morphology. "At least a portion" of the molecular sieve crystals can have a (thin) plate-like morphology and refers to at least about 50%, such as at least 60%, at least 75%, or at least 85% of the molecular sieve crystals can have a (thin) plate-like morphology. "(Thin) plate-like morphology" refers to a crystal that is essentially in the form of a (thin) sheet, such as a disk or rectangular plate, having a first and second major dimension (i.e., the longest dimension of the largest face of the sheet and the dimension of the largest face measured at the midpoint and perpendicular to the longest dimension) of the length (l) and width (b) of the sheet and a third minor dimension (i.e., the minimum dimension measured perpendicular to the largest face at the midpoint of the longest dimension) of the thickness (t) of the sheet that can be referred to as the sheet. The percentage (in % by volume) of the crystals having the morphology and the morphology can be determined by, for example, scanning electron microscopy (SEM) micrographs, such as image analysis using ImageJ software.

[0066] Molecular sieve crystals of the present disclosure having a (thin) plate-like morphology may, for example, have a thickness as small as about 1 nm, such as at least about 5 or 10 nm and at most about 100 nm, such as at most 50 or 25 nm.

[0067] The present disclosure relates in a third aspect to a method for preparing a molecular sieve, in particular a molecular sieve as defined in the first and / or second aspects of the present disclosure, comprising the following steps:

[0068] (a) preparing a mixture comprising water, an oxide source of a tetravalent element (Y), an oxide source of a trivalent element (X),

[0069] 2-ethyl-1,3-dimethylbenzimidazole containing formula I a synthetic mixture of a cationic structure directing agent (Q), a source of fluoride ions (F) and, optionally, a source of hydroxide ions (OH),

[0070]

[0071] (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100-200°C sufficient to form

[0072] time for forming crystals of the molecular sieve;

[0073] (c) recovering at least a portion of the molecular sieve from step (b); and

[0074] (d) Optionally, treating the molecular sieve recovered in step (c) to remove at least a portion of the structure directing agent (Q).

[0075] The structure directing agent (Q) comprises 2-ethyl-1,3-dimethylbenzimidazole of formula I as defined above Cation. The structure directing agent (Q) may be present in any suitable form, for example as a halide, such as fluoride, chloride, iodide or bromide, as a hydroxide or as a nitrate, for example in the form of its hydroxide. The structure directing agent (Q) may be present in the synthesis mixture at a Q / Y molar ratio of 0.05-1.0, such as 0.1-0.8, or 0.2-0.7, or 0.3-0.6, for example 0.5.

[0076] The synthesis mixture comprises at least one source of an oxide of a tetravalent element Y which may be selected from Si and / or Ge, preferably Si. Suitable sources of the tetravalent element Y that may be used to prepare the synthesis mixture depend on the element Y selected. In embodiments where Y is silicon, suitable Si sources (e.g., silicon oxide sources) for use in the process include silicates, such as tetraalkyl orthosilicates such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), fumed silica such as (purchased from Evonik), (available from Cabot) and (purchased from DMS), precipitated silica such as and 340 (available from Evonik) or Alkali metal silicates such as potassium silicate and sodium silicate, and aqueous colloidal suspensions of silicon dioxide, such as those sold by EI du Pont de Nemours under the trade name Sold or marketed by Evonik under the trade name preferably silicates, fumed silica, colloidal silica, precipitated silica, alkali metal silicates, especially silicates. In the embodiment where Y is germanium, a suitable source of Ge includes germanium oxide.

[0077] The synthesis mixture comprises at least one oxide source of a trivalent element X which may be selected from Al and / or B, particularly Al. Suitable sources of the trivalent element X that may be used to prepare the synthesis mixture depend on the element X selected. In embodiments where X is aluminum, suitable Al sources (e.g., alumina sources) for use in the process include aluminum hydroxide, aluminum salts, particularly water-soluble salts such as aluminum sulfate, aluminum nitrate, alkali metal aluminates such as sodium aluminate, and aluminum alkoxides such as aluminum isopropoxide, and hydrated aluminum oxides such as boehmite, gibbsite and pseudoboehmite and mixtures thereof. Other aluminum sources include, but are not limited to, other water-soluble aluminum salts, or metallic aluminum, such as aluminum in fragmented form. Particularly suitable alumina sources are aluminum hydroxide and aluminum alkoxides. In embodiments where X is boron, suitable B sources include boric acid and borates such as sodium tetraborate or borax and potassium tetraborate. Boron sources tend to be more soluble than aluminum sources in hydroxide-mediated synthesis systems.

[0078] Alternatively or in addition to the aforementioned sources of Y and X, sources containing both elements Y and X, such as sources of Si and Al, may be used. Examples of suitable sources containing both elements Y and X include amorphous silica-alumina gel or dried silica-alumina powder, silica-alumina, clays such as kaolin, metakaolin, and zeolites, especially aluminosilicates such as synthetic faujasite and ultrastable faujasite, for example, zeolite Y, ultrastable Y zeolite (USY), zeolite beta, or other large to medium pore molecular sieves or zeolites.

[0079] The synthesis mixture may have a Y / X molar ratio of 5-50, such as 7.5-40 or less than 40, for example 10 or 12-35 or 30 or 25, for example 12.5, 15 or 20.

[0080] In preferred embodiments of this aspect of the invention, Y is Si, X is Al or B and the molecular sieve is an aluminosilicate or borosilicate, especially Y is Si, X is Al and the molecular sieve is an aluminosilicate.

[0081] The synthesis mixture contains at least one fluoride ion (F) source. The fluoride ion (F) source can be any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture. For example, fluoride ions can exist as counterions to the structure directing agent (Q). Non-limiting examples of fluoride ion (F) sources include hydrogen fluoride (HF); salts containing one or more fluoride ions, such as metal fluorides, preferably wherein the metal is an alkali metal or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium or barium, or a metal such as aluminum (AlF3, Al2F6) or tin (SnF2); ammonium fluoride (NH4F); and ammonium difluoride (NH4HF2). Particularly convenient fluoride ion sources are HF, NH4F and NH4HF2, especially HF. Small amounts of fluoride ions (F) can also exist as impurities, for example, in an optional source of alkali metal or alkaline earth metal cations (M). Fluoride ions (F) may be present in a F / Y molar ratio of 0.05-1.0, for example 0.1-0.8, such as 0.15-0.7 or 0.2-0.6, for example 0.5.

[0082] The synthesis mixture may optionally contain at least one halide ion (W) source different from fluoride ion, which may be selected from chloride ion, bromide ion or iodide ion. The halide ion (W) source may be any compound capable of releasing halide ions in the molecular sieve synthesis mixture. For example, halide ions may exist as counterions of the 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 wherein the metal is 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. A small amount of halide ions (W) may also exist as impurities, for example, in an optional source of alkali metal or alkaline earth metal cations (M). The halide ion (W) may exist in a W / Y molar ratio of 0-0.2, such as 0-0.1, for example, less than 0.1 or even 0. Alternatively, the synthesis mixture may be substantially free of halide ions (W).

[0083] Optionally, the synthesis mixture may contain at least one source of hydroxide ions (OH). For example, hydroxide ions may be present as counterions to the structure directing agent (Q) or by using aluminum hydroxide or sodium aluminate as an Al source. Suitable hydroxide ion sources may also be selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; such as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more commonly sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most commonly sodium hydroxide and / or potassium hydroxide. The synthesis mixture may contain a hydroxide ion source in a molar ratio of OH / Y of 0-1.0, such as 0.01-0.8, or 0.1-0.7, for example 0.5. Alternatively, the synthesis mixture may be substantially free of a hydroxide source.

[0084] When the synthesis mixture comprises a hydroxide ion source, the fluoride ion source will at least partially neutralize the hydroxide ions. In a preferred embodiment, the relative amounts of fluoride ions and hydroxide ions can be adjusted so that the synthesis mixture has a pH of less than 10, in particular up to 9, for example about 7, 8 or 9. For example, the pH of the synthesis mixture can be about 7 when the fluoride ion source is HF and can be about 8-9 when the fluoride ion source is NH4F. There is no particular lower limit to the pH of the synthesis mixture. The synthesis mixture typically has a pH of at least 3, for example at least 4, such as at least 5 or 6. In the context of the present disclosure, the pH of the synthesis mixture is measured at 20°C using a pH meter and according to the 2002 IUPAC recommendations (RP Buck et al. (2002) Pure Appl. Chem., Vol. 74 (11), pp. 2169-2200) with an accuracy of ±0.05. A commercially available instrument suitable for pH measurement is the Mettler Toledo FE20 pH meter. pH calibration is performed using a three-point calibration using pH 4.0, pH 7.0, and pH 10.00 standard buffer solutions. Resolution is 0.01 pH, 1 mV, and 0.1°C. Error limits are ±0.01 pH, ±1 mV, and ±0.5°C.

[0085] Optionally, the synthesis mixture may include one or more alkali metal or alkaline earth metal cation (M) sources. If present, M is preferably selected from sodium, potassium, lithium, rubidium, calcium, magnesium, strontium, barium and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. When present, the sodium source may be sodium hydroxide, sodium aluminate, sodium silicate or a sodium salt such as NaCl, NaBr or sodium nitrate. When present, the potassium source may be potassium hydroxide, potassium aluminate, potassium silicate, a potassium salt such as KCl or KBr or potassium nitrate. When present, the lithium source may be lithium hydroxide or a lithium salt such as LiCl, LiBr, LiI, lithium nitrate or lithium sulfate. When present, the rubidium source may be rubidium hydroxide or a rubidium salt such as RbCl, RbBr, RbI or rubidium nitrate. When present, the calcium source may be calcium hydroxide. When present, the magnesium source may be magnesium hydroxide. When present, the strontium source may be strontium hydroxide. When present, the barium source may be barium hydroxide. The alkali metal or alkaline earth metal cation M may also be present in one or more sources of trivalent elements X, such as sodium aluminate, sodium tetraborate, potassium tetraborate and / or one or more sources of tetravalent elements Y, such as potassium silicate and / or sodium silicate. The alkali metal or alkaline earth metal cation (M) source is advantageously soluble in water. The synthesis mixture may comprise the alkali metal or alkaline earth metal cation (M) source in an M / Y molar ratio of 0-1.0, such as 0.01-0.5, for example 0.01-0.2 or 0.15, for example 0 or 0.01-0.1 or even less than 0.1. Alternatively, the synthesis mixture may be substantially free of alkali metal or alkaline earth metal cations (M).

[0086] The synthesis can be carried out with or without the addition of a nucleating seed. If a nucleating seed is added to the synthesis mixture, the seed can have a structure identical or different to that of the molecular sieve of the present disclosure (e.g., the molecular sieve EMM-75 synthesized above), and can be suitably present in an amount of about 0.01 to 10,000 ppm by weight based on the synthesis mixture, such as about 100 to 5,000 ppm by weight based on the synthesis mixture.

[0087] The synthesis mixture is usually with 1-50, as 5-40 or 5-30, for example 5 or 10-15 H o / Y mol ratio comprises water.Depend on the character of each component in basic mixture, the amount of the solvent (for example water from this hydroxide solution and optionally, from the methanol and ethanol of silicon dioxide source hydrolysis) of this basic mixture can be removed so that required solvent / Y mol ratio is obtained to this synthesis mixture.The method that is applicable to reduce solvent content can be included in static or flowing atmosphere such as evaporation under ambient air, dry nitrogen, dry air or by spray drying or freeze drying.When removing too much water in solvent removal process, water can also be added in gained mixture to realize required H o / Y mol ratio.In some instances, when this preparation has enough H water removal is unnecessary during the o / Y mol ratio.

[0088] Carbon in the form of CH2 can be present in various sources of components used to prepare the molecular sieves of the present disclosure, such as a tetravalent element source (silicon dioxide source) or a trivalent element source (alumina source) and incorporated into the resulting molecular sieve framework as a bridging atom. Nitrogen atoms can be incorporated into the framework of the molecular sieve material as a bridging atom after SDA has been removed.

[0089] In one or more aspects, the synthesis mixture, after solvent adjustment (e.g., where a desired water / silica ratio is achieved), can be mixed by mechanical means such as stirring or high shear blending to ensure proper homogenization of the base mixture, for example, using dual asymmetric centrifugal mixing (e.g., a FlackTek high-speed mixer) at a mixing speed of 1000-3000 rpm (e.g., 2000 rpm).

[0090] The synthesis mixture is then subjected to crystallization conditions suitable for forming the molecular sieve material. The molecular sieve material can be crystallized under static or stirred conditions in a suitable reaction vessel, such as a convection oven maintained at a suitable temperature. lined or stainless steel autoclave.

[0091] The crystallization in step (b) of the method is typically carried out at a temperature of 100-200° C., such as 120-180° C., for example 120-150° C., for a time sufficient for crystallization to occur at the temperature used. For example, the crystallization time can be reduced at higher temperatures. For example, the crystallization conditions in step (b) of the method can include heating for 1-100 days, such as 1-50 days, for example 1-30 days, for example at least 1 day or at least 5 days up to a period of 40 days or 30 days. The crystallization time can be determined by methods known in the art, such as by sampling the synthesis mixture at different times and measuring the yield and X-ray crystallinity of the precipitated solid. Unless otherwise specified herein, the temperature measured is the temperature of the surrounding environment of the heated material, for example, the temperature of the atmosphere in which the material is heated.

[0092] The molecular sieve is typically formed in solution and can be recovered by standard means, such as by centrifugation or filtration. The separated molecular sieve can also be washed, recovered by centrifugation or filtration and dried.

[0093] The molecular sieves 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 performed by heating to a temperature in the range of 80-500° C., such as 90-370° C., in an atmosphere such as air, nitrogen, or the like, at atmospheric pressure, subatmospheric pressure, or superatmospheric pressure, and maintaining for 30 minutes to 48 hours. Dehydration can also be performed at room temperature simply by placing the molecular sieve in a vacuum, but longer times are required to obtain a sufficient amount of dehydration.

[0094] As a result of the crystallization process, the recovered product contains at least a portion of the structure directing agent used in the synthesis within its pores. Therefore, the as-synthesized molecular sieve recovered from step (c) can be subjected to heat treatment or other treatment to remove some or all of the SDA introduced into its pores during the synthesis process. The heat treatment (e.g., calcination) of the as-synthesized molecular sieve typically exposes the material to a high temperature in a furnace in an atmosphere selected from air, nitrogen, ozone, or a mixture thereof, sufficient to remove some or all of the SDA. Although pressures below atmospheric pressure can be used for the heat treatment, it is desirable to use atmospheric pressure for convenience reasons. The heat treatment can be carried out at a temperature of up to 925°C, for example, 300-700°C or 400-600°C. The temperature measured is the temperature of the sample's surroundings. The heat treatment (e.g., calcination) can be carried out in a box furnace in dry air that has been exposed to a drying tube containing a desiccant for removing water from the air. The heating is typically carried out for at least 1 minute and is typically no longer than 1 day or at most several days. The heating can initially be carried out under a nitrogen atmosphere and the atmosphere can subsequently be switched to air and / or ozone.

[0095] The molecular sieve can also be subjected to, for example, ion exchange treatment with aqueous ammonium salts, such as ammonium nitrate, ammonium chloride and ammonium acetate, to remove residual alkali metal cations and / or alkaline earth metal cations, if present in the synthesis mixture, and replace them with protons to produce the acid form of the molecular sieve. To the extent required, the original cations of the original material of the synthesis, such as alkali metal cations, can be replaced by other cations by ion exchange. Preferred replacement cations can include hydrogen ions, hydrogen precursors, such as ammonium ions and mixtures thereof. The ion exchange step can be carried out after drying the original molecular sieve of the preparation. The ion exchange step can be carried out before or after the calcining step.

[0096] The molecular sieve may also be subjected to other treatments such as steam treatment and / or washing with solvents. Such treatments are well known to the skilled person and are carried out in order to modify the properties of the molecular sieve as desired.

[0097] The molecular sieves of the present disclosure, after some or all of the SDA has been removed, can be used as adsorbents, catalysts, or catalyst supports in a variety of hydrocarbon conversions, such as converting organic compounds into conversion products. Therefore, in a fourth aspect, the present disclosure relates to a method for converting an organic compound into a conversion product, comprising contacting the organic compound with a molecular sieve prepared according to the first or second aspect of the present disclosure, or according to the third aspect of the present disclosure.

[0098] The molecular sieve materials of the present disclosure (wherein some or all of the SDA is removed) can be used as adsorbents, such as for separating at least one component from a mixture of components in a gas phase or liquid phase that have differential adsorption characteristics with respect to the material. Thus, a mixture of components that have differential adsorption characteristics with respect to the molecular sieve can be contacted with the molecular sieve to selectively adsorb at least one component and partially or substantially completely separate the component from the mixture. For example, in a method for selectively separating one or more desired components of a raw material from the remaining components of the raw material, the raw material can be contacted with an adsorbent comprising a molecular sieve of the present disclosure under effective adsorption conditions to form an adsorbed product and an effluent product. One or more desired components are recovered from the adsorbed product or the effluent product.

[0099] The molecular sieves of the present disclosure (wherein some or all of the SDA is removed) can also be used as catalysts to catalyze a variety of organic compound conversion processes. Examples of chemical conversion processes that are effectively catalyzed by the molecular sieves described herein, alone or in combination with one or more other catalytically active materials including other crystalline catalysts, include those that require catalysts with acid activity. Examples of organic conversion processes that can be catalyzed by the molecular sieves described herein, alone or in combination with one or more other catalytically active materials including other crystalline catalysts, include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, transalkylation, dealkylation, hydrogenation ring opening, disproportionation, oligomerization, dehydrocyclization, methanol to olefins, deNOx applications, and combinations thereof. The conversion of hydrocarbon feeds can be carried out in any convenient manner, for example, in a fluidized bed, moving bed, or fixed bed reactor depending on the type of process desired.

[0100] The molecular sieves of the present disclosure can be formulated into product compositions by combining with other materials, such as binders and / or matrix materials that provide additional hardness to the finished product. These other materials can be inert or catalytically active materials.

[0101] For example, it may be desirable to combine the molecular sieve of the present invention with another material that tolerates the temperature and other conditions used during use. Such materials include synthetic or natural zeolites and inorganic materials such as clays, silica and / or metal oxides such as alumina and mixtures thereof. The metal oxide may be natural or in the form of a gelatinous precipitate or gel comprising a mixture of silica and metal oxides. Using a resistant material in conjunction with the molecular sieve of the present invention, i.e., combining it with or existing in the synthesis process of the prepared molecular sieve, which crystals are active, tends to change the conversion rate and / or selectivity of the catalyst in certain organic conversion processes. Inactive resistant materials are appropriately used as diluents to control the conversion amount in a given process, so that the product can be obtained in an economical and orderly manner without using other measures to control the reaction rate. These materials can be incorporated into natural clays, such as bentonite and kaolin, to improve the crushing strength of the product under commercial operating conditions. The inactive resistant materials, i.e., clays, oxides, etc., are used as binders for the catalyst. Catalysts with good crushing strength can be beneficial because it is desirable to prevent the catalyst from decomposing into powdered materials in commercial applications.

[0102] Natural clays that can be used include the montmorillonite family and the kaolin family, which include sub-bentonites, and kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays, or other clays whose primary mineral components are halloysite, kaolinite, dickite, nacrite, or silica-rich kaolinite. The clay can be used in its original state as initially mined or after calcination, acid treatment, or chemical modification. Binders that can be used in combination with the molecular sieve of the present invention also include inorganic oxides selected from silicon dioxide, zirconium oxide, titanium dioxide, magnesium oxide, beryllium oxide, aluminum oxide, yttrium oxide, gallium oxide, zinc oxide, and mixtures thereof.

[0103] In addition to the aforementioned materials, the molecular sieves of the present disclosure can be composited with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0104] These binder materials are resistant to the temperatures and other conditions that occur in various hydrocarbon separation processes, such as mechanical wear. Therefore, the molecular sieves of the present disclosure can be used in the form of extrudates with a binder. They are typically combined by forming pellets, balls, or extrudates. Extrudates are typically formed by extruding the molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudates. Other treatments such as steam treatment and / or ion exchange may be performed as needed. The molecular sieve may optionally be coated with a surface area of ​​at least 100 m 2 / g, for example at least 200m 2 / g, optional at least 300m 2 / g of adhesive bonding.

[0105] The relative proportions of the molecular sieve and the inorganic oxide matrix can vary widely, with the molecular sieve content ranging from about 1 to 100 weight percent of the composite material and more typically, especially when the composite material is prepared in the form of an extrudate, ranging from about 2 to 95 weight percent, optionally about 20 to 90 weight percent, of the composite material.

[0106] The molecular sieves of the present disclosure can also 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, wherein the hydrogenation-dehydrogenation function is to be achieved. Such hydrogenation components can be incorporated into the composition by one or more of the following methods: co-crystallization; exchange into the composition to the extent that a Group IIIA element, such as aluminum, is present in the structure; or physical mixing with it closely. Such components can also be impregnated in or on the molecular sieve, for example, by treating the molecular sieve with ions containing hydrogenation metals. For example, in the case of platinum, platinum compounds suitable for this purpose include chloroplatinic acid, platinous chloride and various compounds containing platinum amine complexes. Combinations of metals and methods of their introduction can also be used.

[0107] It will be understood by those skilled in the art that the molecular sieves of the present invention may contain impurities, such as amorphous materials, unit cells with different topologies (e.g., quartz or molecular sieves with different framework 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 with different framework types that coexist with the molecular sieves of the present invention are, for example, molecular sieves of IWV framework type, such as ITQ-27. The molecular sieves of the present invention are preferably substantially free of impurities. As used herein, the term "substantially free of impurities" (or alternatively, "substantially pure") means that the molecular sieve material contains a small portion (less than 50% by weight), preferably less than 20% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, and most preferably less than 1% by weight (e.g., less than 0.5% by weight or 0.1% by weight) of such impurities (or "non-EMM-75" materials), wherein the weight percentage (wt%) value is based on the combined weight of the impurities and the pure molecular sieve. The amount of impurities can be suitably determined by powder XRD, rotating electron diffraction and / or SEM / TEM (eg different crystal morphologies).

[0108] The molecular sieves described herein are substantially crystalline. As used herein, the term "crystalline" refers to a crystalline solid form of a material, including but not limited to single-component or multi-component crystal forms, such as solvates, hydrates, and co-crystals. Crystalline can refer to molecules having a regularly repeated and / or orderly arrangement and having a distinguishable lattice. For example, the molecular sieve can have different water contents or solvent contents. Different lattices can be confirmed by solid-state characterization methods such as by XRD (e.g., powder XRD). Other characterization methods known to those of ordinary skill in the relevant art can further help confirm the crystal form and help determine stability and solvent / water content. As used herein, the term "substantially crystalline" refers to a sample of the material where the majority (greater than 50% by weight) is crystalline and the remainder of the sample is amorphous. In one or more aspects, a substantially crystalline sample has at least 95% crystallinity (e.g., 5% amorphous), at least 96% crystallinity (e.g., 4% amorphous), at least 97% crystallinity (e.g., 3% amorphous), at least 98% crystallinity (e.g., about 2% amorphous), at least 99% crystallinity (e.g., 1% amorphous), and 100% crystallinity (e.g., 0% amorphous).

[0109] Various aspects of the present disclosure are described in more detail by specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present disclosure in any way. Those skilled in the relevant art will readily recognize that various parameters can be changed or modified to obtain substantially the same results. Example

[0110] The following further illustrates the present invention without limiting its scope.

[0111] In these examples, X-ray diffraction (XRD) patterns of the as-synthesized and calcined materials were recorded on an X-ray powder diffractometer (Bruker DaVinci D8 Discovery instrument) in continuous mode using Cu Kα radiation with a Vantec 500 detector in Bragg-Bentano geometry over a 2θ range of 4-36 degrees. The interplanar spacings—d spacings—are calculated in angstroms and the relative intensities of the lines are I / I o It is the ratio of the peak intensity to the intensity of the strongest spectral line above the background. The intensity is not corrected for the Lorentz effect and polarization effects. The MDIJade peak search algorithm is used to determine the position of the diffraction peak in 2θ and the relative peak area intensity of the spectral line I / I(o), where Io is the intensity of the strongest spectral line above the background. It should be understood that the diffraction data listed as a single line can be composed of multiple overlapping spectral lines, which may appear as resolved or partially resolved spectral lines under certain conditions, such as differences in crystallographic changes. Crystallographic changes can generally include slight changes in unit cell parameters and / or changes in crystal symmetry without changes in framework connectivity. These minor effects, including changes in relative intensity, may also occur due to 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.

[0112] Scanning electron microscopy (SEM) images of the as-synthesized material were obtained on a Hitachi 4800 scanning electron microscope. SEM images are used to help assess product purity. The presence of distinct crystal morphologies in the SEM images may indicate the presence of impurities in the form of other crystalline materials. This approximate analysis is particularly useful in confirming the presence of relatively small amounts of crystalline impurities that may not be identified on the product XRD pattern.

[0113] The total BET surface area of ​​the material (S BET ) was determined by the BET method described by S. Brunauer, P.H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, Vol. 60, p. 309, incorporated herein by reference, using nitrogen adsorption-desorption at liquid nitrogen temperature. The external surface area (S) of the material 外 ) is obtained by the t-plot method and the micropore surface area of ​​the material (S 微 ) by the total BET surface area (S BET ) minus the surface area (S 外 ) and calculated.

[0114] The micropore volume of the material (V 微 ) and total pore volume (V 总) can be determined using methods known in the relevant art. For example, the micropore and total pore volume of a material can be measured using nitrogen physical adsorption and the data can be analyzed by the t-plot method described in Lippens, BC et al., "Studies on pore systems in catalysts: V. The t method," J. Catal., Vol. 4, p. 319 (1965), which describes micropore and total pore volume methods and is incorporated herein by reference.

[0115] The molar ratios and conditions used for the syntheses of Examples 2-6 and the resulting products are detailed below and summarized in Table 3.

[0116] Example 1: Synthesis of 2-ethyl-1,3-dimethylbenzimidazole Hydroxide (QOH)

[0117] A mixture of 15 g of 2-ethylbenzimidazole, 21 g of potassium carbonate (K2CO3) and 58.3 g of iodomethane in 170 mL of acetonitrile (CH3CN) was heated to 60°C and maintained overnight. The reaction mixture was cooled to room temperature, potassium carbonate was filtered from the solution and the acetonitrile in the filtrate was removed via a rotary evaporator. Chloroform was added to the flask to precipitate the residual potassium salt, and the solution was filtered again. The filtrate in chloroform was rotary evaporated to obtain pure 2-ethyl-1,3-dimethyl-1H-benzo[d]imidazole-3- Iodide.

[0118] Then 2-ethyl-1,5-dimethylbenzimidazole Iodide salts and ion exchange resins IRN78OH hydroxide form was ion exchanged into its hydroxide form with an iodide:resin:water weight ratio of 1:3.5:5. The exchange was performed overnight at room temperature.

[0119] Example 2: Synthesis of EMM-75 with a Si / Al molar ratio of about 15 from TEOS and Al(OH)3

[0120] A mixture of 1.2 g of tetraethyl orthosilicate (TEOS, >99 wt%) and 0.035 g of Al(OH)3 (Sigma, 54 wt% Al2O3) was stirred in 13.5 mL of 2-ethyl-1,3-dimethylbenzimidazole at room temperature. The gel was hydrolyzed in a 4 wt % HF solution for about 2-3 hours, and then 0.12 mL of HF (48 wt % solution) was added to the mixture. The gel was left at room temperature for several days to remove ethanol and water, thereby producing a synthetic mixture having the following composition in terms of molar ratio:

[0121] 10H2O:1SiO2:0.033Al2O3:0.5QOH:0.5HF

[0122] The viscous 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. in a convection oven with rotation (approximately 40 rpm) for 28 days. The product was isolated by filtration, rinsed with deionized water, and dried in a ventilated drying oven at 90° C. The as-synthesized material was then calcined in a box furnace in air at a heating rate of 3° C. / minute to 580° C. This temperature was maintained at 580° C. for 8 hours, after which the box furnace was cooled.

[0123] XRD analysis of the as-synthesized and calcined product showed that the material had a unique powder XRD pattern that could not be matched to any known molecular sieve or zeolite and was designated as the as-synthesized and calcined pure EMM-75 product. Figure 1 and 2 Shown is a powder XRD pattern of the as-synthesized and calcined EMM-75 material of Example 2. Tables 4 and 5 below show a list of peaks and intensities for the as-synthesized and calcined EMM-75 material of Example 2. Figure 3 An SEM image of the as-synthesized product of Example 2 is shown.

[0124] The as-prepared EMM-75 material appears to have monoclinic symmetry (a: b: c: β: 95.000(30)°) and contains about 17% silanol defects, while upon calcination it becomes more symmetrical with an orthorhombic unit cell (a: b: c: ) and the defects are repaired. The calcined EMM-75 material has 48 Si atoms in one unit cell. The calcined EMM-75 material shares a similar structure to MOR zeolite, with a more elliptical 12-membered ring size (12MR: EMM-75 With MOR Compared to) and the narrower 8-membered ring (8R: EMM-75 With MOR compared to). Figure 4 The structure of the EMM-75 material is shown along the

[100] direction.

[0125] The micropore surface area (S) of the calcined form of the EMM-75 material of Example 2 微 ) is 174m 2 / g, its external surface area (S 外 ) is 45m 2 / g, its total volume (V总 ) is 0.23cm 3 / g and its micropore volume (V 微 ) is 0.074c cm 3 / g.

[0126] Example 3: Synthesis of EMM-75 with a Si / Al molar ratio of about 12.5 from TEOS and Al(OH)3

[0127] This example was carried out under conditions similar to those of Example 2, except that the Si / Al ratio was reduced to 12.5, resulting in a synthetic mixture having the following composition in terms of molar ratios:

[0128] 10H2O:1SiO2:0.04Al2O3:0.5QOH:0.5HF.

[0129] After heating at 135°C for 28 days, pure EMM-75 product was obtained as confirmed by its XRD pattern.

[0130] Example 4: Synthesis of EMM-75 with a Si / Al molar ratio of about 15 from TEOS and Al(OiPr)3

[0131] This example was carried out under conditions analogous to Example 2 with a synthesis mixture having the following composition in terms of molar ratios:

[0132] 10H2O:1SiO2:0.033Al2O3:0.5QOH:0.5HF

[0133] The difference is that aluminum isopropoxide (Al(OiPr)3, 98 wt%, Sigma) is used as the Al source. After heating at 135°C for 28 days, its XRD pattern ( Figure 5 ) confirmed that pure EMM-75 product was obtained. Figure 6 An SEM image of the as-synthesized product of Example 3 is shown.

[0134] The micropore surface area (S) of the calcined form of the EMM-75 material of Example 3 微 ) is 155m 2 / g, its external surface area (S 外 ) is 147m 2 / g, its total volume (V 总 ) is 0.73cm 3 / g and its micropore volume (V 微 ) is 0.069cm 3 / g.

[0135] Example 5:Synthesis of EMM-75 with a Si / Al molar ratio of about 20 from TEOS and Al(OiPr)3

[0136] This example was carried out under conditions similar to those of Example 4, except that the Si / Al ratio was increased to 20, resulting in a synthetic mixture having the following composition in terms of molar ratios:

[0137] 10H2O:1SiO2:0.025Al2O3:0.5QOH:0.5HF.

[0138] After heating at 135°C for 28 days, pure EMM-75 product was obtained as confirmed by its XRD pattern.

[0139] Example 6: Synthesis of EMM-75 with a Si / Al molar ratio of about 40 from TEOS and Al(OiPr)3

[0140] This example was carried out under conditions similar to those of Example 4, except that the Si / Al ratio was increased to 20, resulting in a synthetic mixture having the following composition in terms of molar ratios:

[0141] 10H2O:1SiO2:0.0125Al2O3:0.5QOH:0.5HF.

[0142] After heating at 135°C for 28 days, the XRD pattern indicated that the EMM-75 product was obtained with another lamellar phase impurity.

[0143] Table 3

[0144]

[0145] Table 4

[0146]

[0147] Table 5

[0148]

[0149]

[0150] Although the present invention has been described and illustrated with reference to specific embodiments, it will be understood by those skilled in the art that the invention itself is susceptible to many different changes, modifications and variations not specifically described herein. It will also be understood by those skilled in the art that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. Furthermore, all numerical values ​​within the detailed description herein are modified by the value indicated by "about" and take into account experimental errors and variations that would be expected by those skilled in the art.

[0151] If integers or elements are mentioned in the foregoing description as having known, obvious or foreseeable equivalents, such equivalents are incorporated herein as if listed individually. Reference should be made to the claims for determining the true scope of the invention, which should be interpreted as including any such equivalents. The reader should also understand that integers or features of the invention described as preferred, advantageous, convenient, etc. are optional and do not limit the scope of the independent claims. Furthermore, it should be understood that such optional integers or features, while potentially beneficial in some embodiments of the invention, may be undesirable in other embodiments and therefore may not be present.

[0152] Additionally or alternatively, the present invention relates to:

[0153] Embodiment 1. A molecular sieve having, in its calcined form, an X-ray diffraction pattern comprising at least 14 peaks of Table 1.

[0154] Embodiment 2. The molecular sieve of Embodiment 1, having an X-ray diffraction pattern in its calcined form comprising at least 15, preferably at least 16, more preferably at least 17, and most preferably all peaks selected from Table 1.

[0155] Embodiment 3. The molecular sieve of embodiment 1 or 2, having the molecular formula II:

[0156] (m) X2O3:YO2 Formula II,

[0157] Wherein 0.01≤m≤0.1, X is a trivalent element and Y is a tetravalent element.

[0158] Embodiment 4. The molecular sieve of Embodiment 3, wherein X comprises or is aluminum and / or boron, preferably X comprises or is aluminum.

[0159] Embodiment 5. The molecular sieve of Embodiment 3 or 4, wherein Y comprises or is silicon and / or germanium, preferably Y comprises or is silicon.

[0160] Embodiment 6. A molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern comprising at least 9 peaks in Table 2.

[0161] Embodiment 7. The molecular sieve of Embodiment 6, having, in its as-synthesized form, 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.

[0162] Embodiment 8. The molecular sieve of Embodiment 6 or 7, having the molecular formula III:

[0163] (q)Q:(m)X2O3:YO2 Formula III,

[0164] where 0 < q ≤ 0.7, 0.01 ≤ m ≤ 0.1, X is a trivalent element, Y is a tetravalent element and Q contains 2-ethyl-1,3-dimethylbenzimidazole of formula I Cation:

[0165]

[0166] Embodiment 9. The molecular sieve of Embodiment 8, wherein X comprises or is aluminum and / or boron, preferably X comprises or is aluminum.

[0167] Embodiment 10. The molecular sieve of Embodiment 8 or 9, wherein Y comprises or is silicon and / or germanium, preferably Y comprises or is silicon.

[0168] Embodiment 11. The molecular sieve of any one of Embodiments 1-10, wherein at least a portion of the molecular sieve crystals have a plate-like morphology.

[0169] Embodiment 12. The molecular sieve of any one of Embodiments 1-11, which is an aluminosilicate or borosilicate, preferably an aluminosilicate with a Si / Al molar ratio of 5-50.

[0170] Embodiment 13. A method for preparing the molecular sieve of any one of Embodiments 1-12, comprising: (a) preparing a synthesis mixture comprising water, an oxide source of a tetravalent element (Y), an oxide source of a trivalent element (X), a structure-directing agent (Q) containing cations of 2-ethyl-1,3-dimethylbenzimidazole of formula I fluoride ion (F) source, and optionally, a hydroxide ion (OH) source;

[0171]

[0172] (b) heating the synthesis mixture under crystallization conditions including a temperature of 100-200 °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 (Q).

[0173] Embodiment 14. The method of Embodiment 13, wherein the structure-directing agent (Q) is in the form of a halide, hydroxide or nitrate, preferably wherein the structure-directing agent (Q) is in its hydroxide form.

[0174] Embodiment 15. The method of Embodiment 13 or 14, wherein the tetravalent element (Y) comprises silicon and / or germanium, preferably wherein the tetravalent element (Y) is silicon and / or germanium and more preferably silicon.

[0175] Embodiment 16. The method of any one of Embodiments 13-15, wherein the trivalent element (X) comprises aluminum and / or boron, more preferably wherein the trivalent element (X) is aluminum and / or boron, especially aluminum.

[0176] Embodiment 17. The method of any one of Embodiments 13-16, wherein the synthesis mixture has the following composition in terms of molar ratios:

[0177] molar ratio Typical range Preferred range More preferred range Y / X 5-50 10-<40 10-30 Q / Y 0.05-1.0 0.1-0.8 0.2-0.7 F / Y 0.05-1.0 0.1-0.8 0.2-0.7 OH / Y 0-1.0 0.01-0.8 (if OH is present) 0.1-0.7 (if OH is present) <![CDATA[H2O / Y]]> 1-50 5-40 5-30。

[0178] Embodiment 18. The process of any one of Embodiments 13-17, wherein the synthesis mixture is essentially free of alkali metal or alkaline earth metal cations (M), or if some alkali metal or alkaline earth metal cations (M) are present, the M / Y molar ratio is at most 1.0, preferably at most 0.5, in particular at most 0.2, more particularly less than 0.1.

[0179] Embodiment 19. The method of any of embodiments 13-18, wherein the synthesis mixture has a pH of less than 10, preferably at most 9.

[0180] Embodiment 20. The method of any one of embodiments 13-19, wherein the synthesis mixture has a pH of at least 3, preferably at least 4.

[0181] Embodiment 21. A method of converting an organic compound to a conversion product comprising contacting the organic compound with the molecular sieve of any one of Embodiments 1-12.

Claims

1. A molecular sieve having, in its calcined form, an X-ray diffraction pattern comprising at least 14 peaks of Table 1: Table 1 2. The molecular sieve of claim 1 having, in its calcined form, an X-ray diffraction pattern comprising at least 15, preferably at least 16, more preferably at least 17, and most preferably all peaks selected from Table 1.

3. The molecular sieve of claim 1 or 2, having the molecular formula II: (m)X2O3:YO2 Formula II, wherein 0.01≤m≤0.1, X is a trivalent element and Y is a tetravalent element; in particular wherein X comprises or is aluminum and / or boron, preferably X comprises or is aluminum, and Y comprises or is silicon and / or germanium, preferably Y comprises or is silicon.

4. A molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern comprising at least nine of the peaks in Table 2: Table 2 。 5. The molecular sieve of claim 4, having, in its as-synthesized form, 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. The molecular sieve of claim 4 or 5, having the molecular 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 and Q contains 2-ethyl-1,3-dimethylbenzimidazole of formula I Cation: Especially wherein X comprises or is aluminum and / or boron, preferably X comprises or is aluminum, and Y comprises or is silicon and / or germanium, preferably Y comprises or is silicon.

7. The molecular sieve of any one of claims 1 to 6, wherein at least a portion of the molecular sieve crystals have a plate-like morphology.

8. The molecular sieve according to any one of claims 1 to 7, which is an aluminosilicate or a borosilicate, preferably an aluminosilicate having a Si / Al molar ratio of 5 to 50.

9. A method for preparing the molecular sieve according to any one of the preceding claims, comprising: (a) preparing a mixture comprising water, an oxide source of a tetravalent element (Y), an oxide source of a trivalent element (X), and 2-ethyl-1,3-dimethylbenzimidazole of formula I; a synthetic mixture of a cationic structure directing agent (Q), a source of fluoride ions (F) and, optionally, a source of hydroxide ions (OH), (b) heating the synthesis mixture under crystallization conditions including a temperature of 100-200° 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 (Q).

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

11. The method of claim 9 or 10, wherein the tetravalent element (Y) comprises silicon and / or germanium, preferably wherein the tetravalent element (Y) is silicon and / or germanium, more preferably silicon, and wherein the trivalent element (X) comprises aluminum and / or boron, more preferably wherein the trivalent element (X) is aluminum and / or boron, in particular aluminum.

12. The process according to claim 9 , wherein the synthesis mixture has the following composition in terms of molar ratios: 。 13. The process of any one of claims 9 to 12, wherein the synthesis mixture is substantially free of alkali metal or alkaline earth metal cations (M), or, if some alkali metal or alkaline earth metal cations (M) are present, the M / Y molar ratio is at most 1.0, preferably at most 0.5, in particular at most 0.2, more particularly less than 0.

1.

14. The process according to any one of claims 9 to 13, wherein the synthesis mixture has a pH of less than 10, preferably at most 9.

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

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