EMM-74 molecular sieve compositions, synthesis and uses

Abstract

The present invention provides molecular sieves named as EMM-74, characterized by a unique powder XRD pattern, methods of making the same, and uses thereof.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 488,912, filed on March 7, 2023, which is incorporated herein by reference in its entirety. Technical Field

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

[0004] Natural and synthetic molecular sieve materials can be used as adsorbents and have catalytic properties to hydrocarbon conversion reactions. Specific molecular sieves, such as zeolites, AlPO and mesoporous materials, are ordered porous crystalline materials with a clear crystalline structure measured by X-ray diffraction (XRD). Specific molecular sieves are ordered and produce specific identifiable XRD patterns. In specific molecular sieve materials, there can be a large amount of cavities, which can be interconnected by many channels or pores. These holes and pores are uniform in size in specific molecular sieve materials. Because the size of these pores reaches the degree that allows the adsorption of molecules of a specific size and repels those larger molecules, these materials are thus called "molecular sieves" and are used for multiple industrial processes, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization and isomerization.

[0005] Molecular sieves used in catalysis and adsorption include any naturally occurring or synthesized crystalline molecular sieves. Examples of these molecular sieves include ultra-large pore zeolites, large pore zeolites, medium pore zeolites, and small pore zeolites. These zeolites and their isotypes are classified by the International Zeolite Association Structure Committee according to the IUPAC Committee's rules for zeolite nomenclature. According to this classification, framework zeolites and other crystalline microporous molecular sieves with determined structures are assigned three-letter codes and are described in "Atlas of Zeolite Framework Types", compiled 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.

[0006] The idealized inorganic framework structure of zeolite is a silicate framework, in which all tetrahedral atoms are connected to four nearest tetrahedral atoms by oxygen atoms. As used herein, the term "silicate" refers to a substance that contains at least silicon and oxygen atoms (i.e., -O-Si-O-Si-) alternately bonded to each other, and optionally includes other atoms in the inorganic framework structure, including atoms such as 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 part of the lattice sites that would otherwise be occupied by silicon atoms in the "full silica" framework silicate. Therefore, as used herein, the term "framework silicate" refers to an atomic lattice comprising any one of silicate, borosilicate, gallosilicate, ferrosilicate, aluminosilicate, titanosilicate, zinc silicate, vanadium silicate, etc.

[0007] The structure of the framework silicate within a given zeolite determines the size of the pores or channels present therein. The pore or channel size can determine the type of process for which a given zeolite is suitable. Currently, over 200 unique zeolite framework silicate structures are known and recognized by the International Zeolite Association's Structure Committee, defining a variety of pore geometries and orientations.

[0008] The framework silicates of zeolites or molecular sieves are typically characterized by their ring size, wherein the ring size refers to the number of silicon atoms (or substituted atoms, such as those listed above) in the rings that are tetrahedrally coordinated with oxygen atoms to define pores or channels within the zeolite. For example, an "8-ring" zeolite refers to a zeolite whose pores or channels are defined by 8 alternating tetrahedral atoms and 8 oxygen atoms in the rings. Depending on the various structural constraints present in a particular framework silicate, the pores or channels defined within a given zeolite may be symmetrical or asymmetrical.

[0009] Zeolites can be classified as small, medium, large and ultra-large pore structures with pore windows delimited 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, cloverite) and ITV (30R, ITQ-37) framework zeolites. The free pore size of ultra-large pore zeolites is generally greater than about 0.8 nm. Large pore zeolites (12R) include, for example, LTL, MAZ, FAU, EMT, OFF, *BEA, MOR and SFE framework zeolites, such as needle stone, offretite, zeolite L, zeolite Y, zeolite X, ω zeolite, ZSM-2, zeolite T, beta zeolite and SSZ-48. The free pore size of large pore zeolite is generally 0.6nm to 0.8nm.Medium (or medium) pore size zeolite (10R) includes such as MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW and TON framework zeolite, such as ZSM-5, ZSM-11, ZSM-22, MCM-22, silicate-1 and silicate-2.The free pore size of medium pore size zeolite is generally 0.45nm to 0.6nm.Small pore size zeolite (8R) includes such as CHA, RTH, ERI, KFI, LEV and LTA framework zeolite, ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite and ALPO-17. The free pore diameter of small pore zeolites is generally 0.3 nm to 0.45 nm.

[0010] The synthesis of molecular sieve materials typically involves hydrothermal crystallization of a synthesis mixture containing all the element sources present in the molecular sieve (or zeolite), such as a silica source and an alumina source. 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 a specific molecular sieve structure can be formed, thereby promoting the formation of the desired molecular sieve. Various compounds have been used as structure directing agents, including various types 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 in the molecular sieve. Therefore, a "freshly synthesized" molecular sieve will contain a structure directing agent in its pores, and therefore, after crystallization, the "freshly synthesized" (or "freshly manufactured") molecular sieve is typically subjected to a treatment step, such as a calcination step, to remove the structure directing agent.

[0011] For example, U.S. Pat. No. 6,080,382 and G.S. Lee et al. (2002) "Organocations in Zeolite Synthesis: Fused Bicyclo[Im0]Cations and the Discovery of Zeolite SSZ-48", J. Am. Chem. Soc., Vol. 124, pp. 7024-7034 disclose the use of decahydroquinoline. Cations are used as structure-directing agents to prepare molecular sieve SSZ-48, while Y. Luo et al. (2018) "A Facile and Green Method for the Synthesis of SFE Borosilicate Zeolite and Its Heteroatom-Substituted Analogues with Promising Catalytic Performances", Chem. Eur. Jrnl., Vol. 24(2), pp. 306-311 disclose the use of 4-dimethylaminopyridine. SSZ-48 is identified as an SFE-type zeolite containing a one-dimensional 12-membered ring (12MR) channel system with elliptical openings (0.54×0.76 nm). SSZ-48 is generally crystallized in the form of fibrous rods with a crystal size of 0.05-0.25×10 microns or in the form of needles with a uniform size of about 0.05×1 microns. See also P. Wagner et al. (1999) "Electron Diffraction Structure Solution of a Nanocrystalline Zeolite at Atomic Resolution", J. Phys. Chem. B, Vol. 103(39), pp. 8245-8250.

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

[0013] The present disclosure relates to molecular sieves, methods for their manufacture, and uses thereof.

[0014] In a first aspect, the present disclosure is directed 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 the peaks in degrees 2θ of Table 1 below:

[0015] Table 1

[0016]

[0017]

[0018] In a second aspect, the present disclosure relates to a molecular sieve having, in its as-synthesized form (e.g., where the SDA has not been removed), an X-ray diffraction pattern comprising the peaks in degrees 2θ in Table 2 below:

[0019] Table 2

[0020]

[0021] In a third aspect, the present disclosure relates to a method for producing a molecular sieve, in particular the molecular sieve of the first aspect and / or the second aspect, the method comprising the following steps: (a) preparing a synthesis mixture, the synthesis mixture comprising water, a source of a tetravalent element (Y) oxide, optionally a source of a trivalent element (X) oxide, a structure directing agent (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F) and optionally a source of an alkali metal and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation, the at least one cation being selected from 1-methylimidazo[1,2-a]pyridine-1- Cation, 1,2-dimethylimidazo[1,2-a]pyridine-1- cation, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- cation, 1,6-dimethylimidazo[1,2-a]pyridine-1- cation and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-

[0022]

[0023] (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100° C. to 200° C. for a time sufficient to form crystals of the 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).

[0024] In a fourth aspect, the present disclosure relates to a method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with a molecular sieve according to the first or second aspect of the present disclosure or a molecular sieve prepared according to the method of the third aspect of the present disclosure.

[0025] These and other features and attributes of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description below. Of course, it should be understood that the 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 in the Summary of the Invention) may be combined to form a combination of features not specifically described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The powder XRD pattern of the as-synthesized product of Example 2 is shown.

[0027] Figure 2 The powder XRD pattern of the calcined product of Example 2 is shown.

[0028] Figure 3 An SEM image of the as-synthesized product of Example 2 is shown.

[0029] Figure 4 An SEM image of the as-synthesized product of Example 7 is shown.

[0030] Figure 5 An SEM image of the as-synthesized product of Example 14 is shown.

[0031] Figure 6 The powder XRD pattern of the as-synthesized product of Example 17 is shown.

[0032] Figure 7 Powder XRD of the calcined product of Example 17 is shown.

[0033] Figure 8 An SEM image of the as-synthesized product of Example 17 is shown. DETAILED DESCRIPTION

[0034] The present disclosure relates to molecular sieve compositions, methods for their manufacture, and uses thereof. The molecular sieve may be named EMM-74 molecular sieve, EMM-74 zeolite, or EMM-74 material.

[0035] In a first aspect, the present disclosure is directed to a molecular sieve having, in its calcined form (e.g., wherein at least a portion of the SDA has been removed by heat or other treatment), an X-ray diffraction pattern comprising the peaks in Table 1 below:

[0036] Table 1

[0037]

[0038]

[0039] In another embodiment, the molecular sieve, in its calcined form, may have an X-ray diffraction pattern comprising the peaks in Table 1A below, wherein the d-spacing values have deviations determined based on corresponding deviations of ±0.20 degrees 2-theta when converted to corresponding values of d-spacings using Bragg's law:

[0040] Table 1A

[0041]

[0042] For example, the molecular sieve may be an aluminosilicate molecular sieve or a borosilicate molecular sieve having, in its calcined form, an X-ray diffraction pattern comprising the peaks in the following Table 1B (aluminosilicates) and Table 1C (borosilicates), respectively, wherein the d-spacing values, when converted to corresponding values of d-spacings using Bragg's law, have deviations determined based on corresponding deviations of ±0.20 2θ degrees:

[0043] Table 1B

[0044]

[0045]

[0046] Table 1C

[0047]

[0048] The XRD patterns with the XRD peaks described herein were obtained using Cu(K α )radiation.

[0049] In one or more other embodiments, the molecular sieve in its calcined form may have a micropore volume of 0.05 cc / g to 0.25 cc / g, such as 0.07 cc / g to 0.2 cc / g, for example 0.12 cc / g.

[0050] In one or more other embodiments, the molecular sieve may have a 100 m 2 / g to 700m 2 / g, such as 200m2 / g to 500m 2 / g, for example 302m 2 / g of micropore surface area, and / or 5m 2 / g to 200m 2 / g, such as 10m 2 / g to 100m 2 / g, for example 53m 2 / g of external surface area.

[0051] In one or more other embodiments, the molecular sieve in its calcined form may optionally be represented by the formula V:

[0052] (m) X2O3:YO2 (Formula V),

[0053] Wherein 0≤m≤0.1, X is a trivalent element, and Y is a tetravalent element. Y may comprise one or more of Si, Ti, Zr, Sn and Ge. For example, Y may comprise Si and / or Ge or be Si and / or Ge, for example, Y may comprise Si or be Si. X may comprise one or more of Al, B, Fe or Ga. In particular, X may comprise Al and / or B or be Al and / or B, for example, X may comprise Al or be Al. In an embodiment where Y is Si and X is Al, the molecular sieve is an aluminosilicate. In an embodiment where Y is Si and X is B, the molecular sieve is a borosilicate. In an embodiment where Y is Si and X is a mixture of Al and B, the molecular sieve is an aluminoborosilicate. The oxygen atom in Formula V may be replaced by a carbon atom (for example, in the form of CH2), which may be from a source of components used to prepare the freshly manufactured molecular sieve. The oxygen atom in Formula V may also be replaced by a nitrogen atom, for example, by a nitrogen atom after SDA has been removed. Formula V may represent the framework of a typical molecular sieve as defined in the present disclosure in its calcined form and is not intended to be the only representative of such molecular sieves. After appropriate treatment to remove SDA and impurities, the molecular sieve in its calcined form may contain SDA and / or impurities, which are not illustrated in Formula V. In addition, Formula V does not include protons and charge-compensating ions that may be present in the calcined molecular sieve.

[0054] The variable m represents the molar ratio relationship of X2O3 to YO2 in Formula V. 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., the molar ratio of Si / Al is 20). m can vary from 0 to 0.1, such as at least 0.0017, or at least 0.005, or at least 0.007, or at least 0.01 to at most 0.1, or at most 0.07, or at most 0.05, for example, 0.001 or 0.005 to 0.05 or 0.025. The molar ratio of Y to X can be from 5 to infinity (corresponding to a silicate product), such as at least 5, or at least 7, or at least 10, or at least 15 and up to infinity, or up to 300, or up to 100, or up to 75, or up to 50, for example, from 10 or 15 or 20 to infinity or 300 or 100 or 75.

[0055] In a second aspect, the present disclosure relates to a molecular sieve, in particular a molecular sieve as defined in the first aspect, which, in its as-synthesized form (e.g., wherein the SDA has not been removed), has an X-ray diffraction pattern comprising the peaks in degrees 2θ shown in Table 2 below:

[0056] Table 2

[0057]

[0058] In another embodiment, the molecular sieve, in its as-synthesized form, may have an X-ray diffraction pattern comprising the peaks in Table 2A below, wherein the d-spacing values have deviations determined based on corresponding deviations of ±0.20 degrees 2-theta when converted to corresponding values of d-spacings using Bragg's law:

[0059] Table 2A

[0060]

[0061]

[0062] For example, the molecular sieve may be an aluminosilicate molecular sieve or a borosilicate molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern comprising the peaks in the following Table 2B (aluminosilicates) and Table 2C (borosilicates), respectively, wherein the d-spacing values, when converted to corresponding values of d-spacings using Bragg's law, have deviations determined based on corresponding deviations of ±0.20 2θ degrees:

[0063] Table 2B

[0064]

[0065] Table 2C

[0066]

[0067]

[0068] An XRD pattern having the XRD peaks described herein uses Cu(K α ) radiation.

[0069] In one or more other embodiments, the molecular sieve in its as-synthesized form may optionally be represented by the empirical formula of Formula VI:

[0070] (q)Q:(m)X2O3:YO2 (Formula VI),

[0071] where 0 < q ≤ 0.7; 0 ≤ m ≤ 0.1; Q comprises at least one cation selected from the 1-methylimidazo[1,2-a]pyridin-1- cation of Formula I, the 1,2-dimethylimidazo[1,2-a]pyridin-1- cation of Formula II, the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridin-5- cation of Formula III, the 1,6-dimethylimidazo[1,2-a]pyridin-1- cation of Formula IV, and the 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridin-4-

[0072]

[0073]

[0074] X is a trivalent element as defined for Formula V, and Y is a tetravalent element as defined for Formula V. Formula VI may represent the framework of a typical molecular sieve in its as-synthesized form and thus containing a structure directing agent (Q), and is not meant to be the sole representation of the molecular sieve. The molecular sieve in its as-synthesized form may contain impurities not accounted for in Formula VI. In addition, Formula VI does not include protons and charge compensating ions that may be present in the as-synthesized molecular sieve.

[0075] The variable m represents the molar ratio relationship of X2O3 to YO2 in Formula VI. The value of the variable m in Formula VI is the same as those described herein for Formula V.

[0076] The variable q represents the molar ratio relationship of Q to YO2 in Formula VI. For example, when q is 0.1, the molar ratio of Q to YO2 is 0.1. The molar ratio of Q to YO2 can be greater than 0 to 0.7, such as 0.1 to 0.6, for example 0.1 to 0.5.

[0077] In another embodiment, the framework structure of the molecular sieve of the first aspect and / or the second aspect of the present disclosure (whether in freshly synthesized or calcined form) can be identified as an SFE framework type. In particular, the framework structure of the molecular sieve of the present disclosure can be identified as having a size of 12-ring pore channel (12MR).

[0078] In another embodiment, at least a portion of the molecular sieve crystals of the present disclosure (whether in a freshly synthesized form or a calcined form) can have a rod-like morphology. "At least a portion" of the molecular sieve crystals can have a rod-like morphology, meaning that at least about 50%, such as at least 60%, at least 75% or at least 85% of the molecular sieve crystals can have a rod-like morphology. "Rod-like morphology" refers to a substantially elongated particle such as a rod or cylinder, particularly a crystal having a long dimension (i.e., the longest dimension) along the c-axis and a short dimension perpendicular to the long dimension (i.e., the minimum dimension measured in the middle of the long dimension and perpendicular to the long dimension), wherein the long dimension can be referred to as the length (l) of the crystal, and the short dimension can be referred to as the width, thickness or diameter (d) of the crystal. The morphology of the crystal and the percentage (such as volume %) of the crystal with the morphology can be determined, for example, by image analysis of a scanning electron microscope (SEM) micrograph, for example, using ImageJ software to determine.

[0079] The molecular sieve crystals having a rod-like morphology according to the present disclosure may typically have a length (l) of 30 nm to 10 micrometers (μm), particularly at least 50 nm, or at least 75 nm, or at least 100 nm and at most 5 μm, or at most 1 μm, or at most 600 nm, such as at least 100 or 150 or 200 nm and at most 1 μm or 500 nm or 400 nm, for example about 300 nm, 200 nm or 100 nm, and a width, thickness or diameter (d) of 20 nm to 200 nm, particularly at least 25 nm, or at least 30 nm, or at least 40 nm and at most 100 nm, or at most 75 nm, or at most 60 nm, such as at least 30 or 40 or 45 nm and at most 100 or 75 or 60 nm, for example about 30 nm to 50 nm. Molecular sieve crystals according to the present disclosure having a rod-like morphology are defined as having an aspect ratio of the length to diameter ratio (l / d) of the crystals that can typically be from 1 to 10, particularly greater than 1, or at least 2, or at least 3 and less than 10, or at most 9, or at most 8, such as from 2 to 9, or from 3 to 8, or from 2 to 5, or from 4 to 7, for example about 2, 3, 4, 5 or 6.

[0080] In another embodiment, at least a portion of the molecular sieve crystals of the present disclosure (whether in a freshly synthesized form or a calcined form) can have a plate-like morphology. "At least a portion" of the molecular sieve crystals can have a plate-like morphology, meaning that at least about 50%, such as at least 60%, at least 75% or at least 85% of the molecular sieve crystals can have a plate-like morphology. "Plate-like morphology" refers to a crystal that is essentially a thin sheet, such as a disc or rectangular plate, having a first major dimension and a second major dimension that can be referred to as the length (l) and width (b) of a thin sheet (i.e., the longest dimension of the largest face of the thin sheet and the dimension of the largest face in the middle and perpendicular to the longest dimension), and a smaller third dimension that can be referred to as the thickness (t) of the plate (i.e., the minimum dimension measured in the middle of the longest dimension and perpendicular to the largest face). The morphology of the crystal and the percentage (such as volume %) of the crystals having the morphology can be determined, for example, by image analysis of a scanning electron microscope (SEM) micrograph, for example, using ImageJ software to determine.

[0081] The molecular sieve crystals having a plate-like morphology according to the present disclosure may have a length to width ratio (l / b) of 1 to 5, such as 1 to 4 or 1 to 3, for example about 1, 1.5 or 2, and a length to thickness ratio (l / t) of greater than 1 to 10, such as 2 to 8 or 3 to 6, for example about 4 or 5. The width to thickness ratio (b / t) may vary accordingly, for example, greater than 1 to 10, such as 1.5 to 8 or 2 to 6, for example, 2 or 2.5 to 5. In a more specific embodiment, the molecular sieve crystals having a plate-like morphology according to the present disclosure may have a length (l) of 75 nm to 1 μm, such as at least 100 nm and at most 500 nm, or at most 300 nm, or at most 200 nm, for example about 100 nm or 150 nm, and a thickness (t) of 5 nm to 60 nm, such as 10 or 15 nm to 40 or 50 nm, for example about 20 or 30 nm. For example, the molecular sieve crystals may have a length (l) of about 100 nm to 200 nm, a width (b) of about 50 nm to 150 nm, and a thickness (t) of about 20 nm to 30 nm.

[0082] Rod and plate morphologies are particularly advantageous in catalytic and adsorption applications, compared to fiber-like (or fibrous) morphologies, which typically have aspect ratios (l / d) greater than 10. Indeed, due to their shorter diffusion lengths, the diffusion rate through the longest dimension of the zeolite crystal is faster in rod- and plate-like particles than in fiber-like (or fibrous) particles, which have much longer diffusion lengths. Furthermore, fibrous crystals have raised concerns about the health effects of long-term inhalation.

[0083] Therefore, in another aspect, the present disclosure relates to a molecular sieve of the SFE framework type, characterized by a rod-like or plate-like morphology, particularly a plate-like morphology.

[0084] In a third aspect, the present disclosure relates to a method for producing a molecular sieve, in particular a molecular sieve as defined in the first aspect and / or the second aspect of the present disclosure, the method comprising the following steps:

[0085] (a) preparing a synthesis mixture comprising water, a source of a tetravalent element (Y) oxide, optionally a source of a trivalent element (X) oxide, a structure directing agent (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F), and optionally a source of an alkali metal and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 1-methylimidazo[1,2-a]pyridine-1- Cation, 1,2-dimethylimidazo[1,2-a]pyridine-1- cation, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- cation, 1,6-dimethylimidazo[1,2-a]pyridine-1- cation and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-

[0086]

[0087] (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100° C. to 200° C. for a time sufficient to form crystals of the molecular sieve;

[0088] (c) recovering at least a portion of the molecular sieve from step (b); and

[0089] (d) optionally treating the molecular sieve recovered in step (c) to remove at least a portion of the structure directing agent (Q).

[0090] The structure directing agent (Q) may be selected from the cations of formula I, formula II and / or formula III as defined above, in particular, it may be 1-methylimidazo[1,2-a]pyridine-1- Cation, 1,2-dimethylimidazo[1,2-a]pyridine-1- cation, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- cation, 1,6-dimethylimidazo[1,2-a]pyridine-1- cation or 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4- 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 0.01 to 1.0, such as 0.05 to 1.0, or at least 0.1, or at least 0.15 and at most 0.8, or at most 0.7, or at most 0.6, for example 0.1 or 0.15 to 0.7 or 0.6, for example 0.15 to 0.5. Without wishing to be bound by theory, it has been noted that the 1-methylimidazo[1,2-a]pyridine-1- Cation, 1,2-dimethylimidazo[1,2-a]pyridine-1- cation and 1,6-dimethylimidazo[1,2-a]pyridine-1- The structure directing agent (Q) of at least one cationic cation appears to be advantageous for synthesizing the molecular sieve crystals with rod-like morphology disclosed herein, and the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- The presence of at least one cationic structure directing agent (Q) appears to facilitate the synthesis of the disclosed molecular sieve crystals having a plate-like morphology.

[0091] The synthesis mixture comprises at least one source of an oxide of a tetravalent element Y, and element Y may be selected from Si, Ti, Zr, Sn, Ge, and mixtures thereof. Preferably, Y comprises Si and / or Ge, such as Si, and more preferably, Y is Si and / or Ge, such as Si. Suitable sources of tetravalent element Y that can be used to prepare the synthesis mixture depend on the element Y selected. In embodiments where Y is silicon, sources of Si (e.g., silicon oxide sources) suitable for use in the method include silicates, such as tetraalkyl orthosilicates such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS), fumed silica such as (commercially available from Evonik), (commercially available from Cabot) and (commercially available from DMS), precipitated silica such as and 340 (available from Evonik), alkali metal silicates such as potassium silicate and sodium silicate, and aqueous colloidal silica suspensions, such as those sold by Grace under the trade name Sold or marketed by Evonik under the trade name Aqueous colloidal silica suspensions for sale; preferably silicates, fumed silica, precipitated silica, faujasite, alkali metal silicates and colloidal silica. In embodiments where Y is germanium, suitable Ge sources include germanium oxide. In embodiments where Y is titanium, suitable Ti sources include titanium dioxide and titanium tetraalkoxides, such as titanium (IV) tetraethoxide, and titanium (IV) tetrachloride. In embodiments where Y is tin, suitable Sn sources include tin chloride and tin alkoxides, such as tin ethoxide and tin isopropoxide. In embodiments where Y is zirconium, suitable Zr sources include zirconium chloride and zirconium alkoxides, such as zirconium ethoxide and zirconium isopropoxide.

[0092] The synthesis mixture comprises at least one source of an oxide of a trivalent element X, which may be selected from the group consisting of Al, B, Fe, Ga, and mixtures thereof, preferably comprising Al and / or B, such as Al, more preferably Al and / or B, such as Al. Suitable sources of trivalent elements X that may be used to prepare the synthesis mixture depend on the element X selected. In embodiments where X is aluminum, suitable sources of Al (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, sodium aluminate, aluminum alkoxides such as aluminum isopropoxide, or aluminum metal such as aluminum in the form of crumbs. Particularly suitable sources of alumina are aluminum hydroxide, water-soluble salts such as aluminum sulfate, aluminum nitrate, and alkali metal aluminates such as sodium aluminate and potassium aluminate. In embodiments where X is boron, suitable B sources include boric acid and borates such as sodium tetraborate or borax and potassium tetraborate. In hydroxide-mediated synthesis systems, boron sources are often more soluble than aluminum sources. In embodiments where X is gallium, suitable Ga sources include sodium gallate, potassium gallate, and gallium salts such as gallium chloride, gallium sulfate, and gallium nitrate. In embodiments where X is iron, suitable Fe sources include ferric chloride, ferric nitrate, and iron oxides.

[0093] Alternatively, or in addition to the previously mentioned sources of Y and X, sources containing both elements Y and X, such as Si and Al sources, may be used. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gel or dried silica-alumina powder, silica-alumina, clays such as kaolin, metakaolin, and zeolites, particularly aluminosilicates such as synthetic faujasite and ultrastable faujasite, for example, zeolite Y, ultrastable Y (USY), zeolite beta, or other large to medium pore zeolites.

[0094] The Y / X molar ratio of the synthesis mixture can be from 5 to infinity (corresponding to the silicate product), such as at least 5 or at least 7 or at least 10 and up to infinity, or up to 300, or up to 100, or up to 75, or up to 50, for example 10 or 15 or 20 to infinity or 300 or 100 or 50.

[0095] In a preferred embodiment, Y is Si, optionally X is Al and / or B, and the molecular sieve is a silicate, aluminosilicate, borosilicate or aluminoborosilicate. In another preferred embodiment, Y is Si, optionally X is Al and / or B, and the molecular sieve is aluminosilicate, borosilicate or aluminoborosilicate.

[0096] 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 typically sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most typically sodium hydroxide and / or potassium hydroxide. The synthesis mixture may comprise a hydroxide ion source having an OH / Y molar ratio of 0 to 1.0, such as 0.05 to 0.8 or 0.1 to 0.7 or 0.15 to 0.6, for example 0.25 to 0.5. Alternatively, the synthesis mixture may be substantially free of a hydroxide source.

[0097] 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, and mixtures thereof, preferably sodium and / or potassium, more preferably sodium. When present, the sodium source may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or a sodium salt such as NaCl, NaBr, or sodium nitrate. When present, the potassium source may be potassium hydroxide, potassium aluminate, potassium silicate, a potassium salt such as KCl, KBr, or potassium nitrate. When present, the lithium source may be lithium hydroxide, or a lithium salt such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. When present, the rubidium source may be rubidium hydroxide, or a rubidium salt such as RbCl, RbBr, RBI, or rubidium nitrate. When present, the calcium source may be, for example, calcium hydroxide. When present, the magnesium source may be, for example, magnesium hydroxide. The alkali 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 in one or more sources of tetravalent elements Y, such as potassium silicate and / or sodium silicate. The synthesis mixture may comprise a source of alkali metal or alkaline earth metal cations (M) in a molar ratio M / Y of 0 to 1.0, such as 0.05 to 0.5 or 0.05 to 0.2, for example 0.1 to 0.15. Alternatively, the synthesis mixture may be substantially free of alkali metal or alkaline earth metal cations (M).

[0098] The synthesis mixture may optionally contain at least one fluoride ion (F) source. The fluoride ion (F) source may be any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture. For example, fluoride ions may be present 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 bifluoride (NH4HF2). Particularly convenient fluoride ion sources are HF, NH4F and NH4HF2, in particular HF. Small amounts of fluoride ions (F) may also be present as impurities, for example in the optional alkali metal or alkaline earth metal cation (M) source. Fluoride ions (F) may be present in a F / Y molar ratio of 0 to 1.0, such as 0 or 0.1 to 0.8, such as 0.2 to 0.7 or 0.3 to 0.6, such as 0.4 or 0.5. Alternatively, the synthesis mixture may be substantially free of fluoride ions (F).

[0099] The synthesis mixture may optionally further contain at least one halide ion (W) source different from fluoride ion, which may be selected from chloride, bromide or iodide. 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 (HCl), hydrogen bromide (HBr), hydrogen iodide (HI); ammonium halides (e.g., NHCl, NBr, NHI); salts containing one or more halide ions, such as metal halides, preferably wherein the metal is 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 alkali metal or alkaline earth metal cation (M) source. The halide ion (W) may exist in a W / Y molar ratio of 0 to 0.2, such as 0 to 0.1, for example, less than 0.1 or even 0. In a preferred embodiment, the synthesis mixture may be substantially free of halide ions (W).

[0100] The synthesis can be carried out with or without the addition of nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds can be of the same or different structure as the molecular sieve of the present disclosure, such as the EMM-74 material obtained by a previous synthesis, and can suitably be present in an amount of from about 0.01 ppm by weight to about 10,000 ppm by weight relative to the synthesis mixture, such as from about 100 ppm by weight to about 5,000 ppm by weight of the synthesis mixture.

[0101] The synthesis mixture typically comprises H2O / Y molar ratio of 1 to 100, such as 5 to 80 or 7.5 to 50, for example 7.5 or 10 to 40 or 35 water. Depending on the properties of the components in the basic mixture, a certain amount of solvent (e.g., water from hydroxide solution, and optionally methanol and ethanol from hydrolysis of a silica source) can be removed from the basic mixture so that the synthesis mixture reaches the desired solvent and Y molar ratio. Suitable methods for reducing solvent content can include evaporation under a static or flowing atmosphere, such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. When removing excessive water in the solvent removal process, water can be added to the resulting mixture to achieve the desired H2O / Y molar ratio. In certain embodiments, when the preparation has enough H2O / Y molar ratios, it is not necessary to remove water.

[0102] Carbon in the form of CH2 may be present in various component sources 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 molecular sieve framework as a bridging atom. After SDA has been removed, nitrogen atoms may be incorporated into the framework of the molecular sieve framework as bridging atoms.

[0103] In one or more aspects, the synthesis mixture after solvent adjustment (e.g., where a desired water to silica ratio is achieved) can be mixed by mechanical means such as stirring or high shear mixing to ensure proper homogenization of the base mixture, for example, using dual asymmetric centrifugal mixing (e.g., a FlackTek speedmixer) at a mixing speed of 1000 rpm to 3000 rpm (e.g., 2000 rpm).

[0104] The synthesis mixture is then subjected to crystallization conditions suitable for the formation of the molecular sieve. Crystallization of the molecular sieve can be carried out under static or stirred conditions in a suitable reaction vessel, such as a convection oven maintained at an appropriate temperature. The process is carried out in a lined autoclave or a stainless steel autoclave.

[0105] The crystallization in step (b) of the method is typically carried out at a temperature of 100°C to 200°C, such as 120°C to 180°C, preferably 150°C to 170°C, for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be reduced. For example, the crystallization conditions in step (b) of the method can include heating for 1 to 100 days, such as 1 to 50 days, such as 1 to 30 days, such as at least 1 day or at least 4 days or at least 10 days up to a period of 40 days or 30 days or 21 days. The crystallization time can be determined by methods known in the art, such as by sampling the synthesis mixture at different times and determining 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, such as the temperature of the atmosphere in which the material is heated.

[0106] Typically, the molecular sieve is formed in solution and can be recovered by standard methods, such as by centrifugation or filtration. The separated molecular sieve can also be washed, recovered by centrifugation or filtration and dried.

[0107] When used as an adsorbent or catalyst in an organic compound conversion process, the molecular sieve of the present disclosure can be at least partially dehydrated (e.g., dried). This can be achieved by heating to a temperature in the range of 80°C to 500°C, such as 90°C to 370°C, for 30 minutes to 48 hours in an atmosphere such as air, nitrogen, and at atmospheric, subatmospheric, or superatmospheric pressures. Dehydration can also be performed simply by placing the molecular sieve in a vacuum at room temperature, but a longer time is required to achieve sufficient dehydration.

[0108] 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 freshly synthesized molecular sieve recovered from step (c) can be subjected to heat treatment or other treatment to remove some or all of the SDA incorporated into its pores during the synthesis process. Heat treatment (e.g., calcination) of the freshly synthesized molecular sieve typically subjects 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 subatmospheric pressures can be used for heat treatment, atmospheric pressure is ideal for convenience. Heat treatment can be carried out at a temperature of up to 925°C, for example, from 300°C to 700°C or from 400°C to 600°C. The temperature measured is the temperature of the surrounding environment of the sample. Heat treatment (e.g., calcination) can be carried out in dry air in a box furnace, which is subjected to a drying tube containing a desiccant to remove water from the air. Heating is typically performed for at least 1 minute, usually not more than 1 day or at most several days. Heating may be performed first under a nitrogen atmosphere, and then the atmosphere may be switched to air and / or ozone.

[0109] The molecular sieve can also be subjected to ion exchange treatment, for example, with an aqueous solution of 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, thereby producing the molecular sieve in acid form. To the extent required, the original cations of the just-synthesized material, such as alkali metal cations, can be replaced with 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 the molecular sieve just manufactured is dried. The ion exchange step can be carried out before or after the calcining step.

[0110] Optionally, aluminum atoms can be introduced into the molecular sieve framework (wherein some or all of the SDA has been removed) during the exchange process after the hydrothermal synthesis reaction. Framework silicates containing boron atoms (e.g., borosilicates) are particularly effective for exchanging with aluminum atoms. This exchange process may include subjecting the molecular sieve to an aluminum source under conditions sufficient to exchange at least a portion of, and up to substantially all of, the boron atoms in the framework silicate with aluminum atoms. The aluminum source is, for example, an aqueous solution containing an aluminum salt. For example, a calcined molecular sieve containing boron can be converted into an aluminosilicate molecular sieve by heating the calcined molecular sieve (e.g., in a sealed autoclave in a conventional oven at 100°C, or in an open system at boiling temperature) using aluminum sulfate, aluminum nitrate, aluminum chloride, and / or aluminum acetate solution. The aluminum-treated molecular sieve can then be recovered by filtration and washed with deionized water.

[0111] The molecular sieve may also be subjected to other treatments, such as steam treatment and / or washing with a solvent. These treatments are well known to those skilled in the art and are carried out in order to modify the properties of the molecular sieve as desired.

[0112] The molecular sieves of the present disclosure from which 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 the conversion of organic compounds into conversion products. In a fourth aspect, the present disclosure is therefore directed to a method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with a molecular sieve according to the first or second aspect of the present disclosure, or a molecular sieve prepared according to the method of the third aspect of the present disclosure.

[0113] The molecular sieves 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 gaseous or liquid components having different adsorption characteristics for the material. Thus, at least one component can be partially or substantially completely separated from a mixture of components having different adsorption characteristics for the molecular sieve by contacting the mixture with the molecular sieve to selectively adsorb one component. For example, in a process 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 the molecular sieve of the present disclosure under effective adsorption conditions to form an adsorbed product and an effluent product. The one or more desired components are recovered from the adsorbed product or the effluent product.

[0114] Molecular sieves of the present disclosure (wherein some or all of SDA is removed) can also be used as catalysts to catalyze a variety of organic compound conversion processes. Examples of chemical conversion processes effectively catalyzed by molecular sieves as herein described, alone or in combination with one or more other catalytically active materials (including other crystalline catalysts), include those chemical conversion processes that require catalysts with acid activity. Examples of organic conversion processes that molecular sieves as herein described can catalyze 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 feedstock can be carried out in any convenient mode, for example, in fluidized bed, moving bed or fixed bed reactors, depending on the required process type.

[0115] 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 final product. These other materials can be inert materials or catalytically active materials.

[0116] For example, what can be satisfied is another material that is incorporated into the molecular sieve of the present invention and tolerates the temperature and other conditions used during use. These materials include synthetic or naturally occurring zeolites and inorganic materials, such as clay, silica and / or metal oxides (such as aluminum oxide) and mixtures thereof. The metal oxide can be naturally occurring, or in the form of a gelatinous precipitate or gel, including a mixture of silica and metal oxides. The use of a tolerant material in conjunction with (i.e., in combination with) the molecular sieve present during the synthesis of the molecular sieve disclosed herein or just manufactured (the crystal is active) can change the conversion rate and / or selectivity of the catalyst in a specific organic conversion process. Inactive tolerant materials are suitable for use 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 adopting other methods to control the reaction rate. These materials can be incorporated into naturally occurring clays, such as bentonite and kaolin, to improve the crushing strength of the product under commercial operating conditions. The inactive tolerant materials, i.e., clays, oxides, etc., are used as binders for catalysts. A catalyst having good crush strength can be beneficial because it is necessary to prevent the catalyst from breaking down into a powdery material during commercial use.

[0117] Naturally occurring clays that can be used include the montmorillonite and kaolin families, 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 auxite. These clays can be used in their original state as initially mined, or after calcination, acid treatment, or chemical modification. Binders that can be used in combination with the molecular sieves of the present invention also include inorganic oxides selected from the group consisting of silicon dioxide, zirconium oxide, titanium dioxide, magnesium oxide, beryllium oxide, aluminum oxide, yttrium oxide, gallium oxide, zinc oxide, and mixtures thereof.

[0118] In addition to the materials described above, the molecular sieves of the present disclosure may be composited with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0119] 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 containing a binder. They are typically bonded by forming pellets, spheres, or extrudates. Extrudates are typically formed by extruding the molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudate. Further treatments, such as steam treatment and / or ion exchange, can be performed as needed. The molecular sieve can optionally be bonded with a surface area of at least 100 m 2 / g, for example at least 200m 2 / g, optionally at least 300m 2 / g of adhesive bonding.

[0120] The relative proportions of the molecular sieve and the inorganic oxide matrix can vary widely, with the molecular sieve content ranging from about 1 weight percent to about 100 weight percent, and particularly when preparing the composite material in the form of an extrudate, more typically ranging from about 2 weight percent to about 95 weight percent, optionally from about 20 weight percent to about 90 weight percent of the composite material.

[0121] In the case of performing the hydrogenation-dehydrogenation function, the molecular sieve 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. These hydrogenation components can be incorporated into the composition by one or more of the following processes: co-crystallization; exchange into the composition to the extent that the group IIIA element (e.g., aluminum) is in the structure; or closely physically mixed with it. These 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.

[0122] It will be understood by those skilled in the art that the molecular sieve of the present invention may contain impurities, such as amorphous materials, unit cells with different topological structures (e.g., quartz or molecular sieves of different framework types, which may or may not affect the performance of the resulting catalyst) and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). Typical examples of molecular sieves of different framework types coexisting with the molecular sieve of the present invention are, for example, ferrierite or FER framework-type molecular sieves, such as ZSM-35. The molecular sieve of the present invention is preferably substantially free of impurities. The term "substantially free of impurities" (or alternatively, "substantially pure") as used herein refers to a molecular sieve containing a small proportion (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, most preferably less than 1% by weight (e.g., less than 0.5% by weight or 0.1% by weight) of such impurities (e.g., "non-EMM-74 material"), the weight percentage (wt%) value being relative to the total 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).

[0123] The molecular sieves described herein are substantially crystalline. As used herein, the term "crystalline" refers to the crystalline solid form of a material, including but not limited to single-component or multi-component crystal forms, such as solvates, hydrates, and co-crystals. Crystallization can refer to molecules with regular repetition and / or orderly arrangement and with distinguishable lattices. For example, the molecular sieve can have different water or solvent contents. Different lattices can be identified by solid-state characterization methods such as XRD (e.g., powder XRD). Other characterization methods known to those of ordinary skill in the relevant art can further help identify crystalline forms and help determine stability and solvent / water content. As used herein, the term "substantially crystalline" refers to that the majority (greater than 50% by weight) of the material sample 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 form), at least 96% crystallinity (e.g., 4% amorphous form), at least 97% crystallinity (e.g., 3% amorphous form), at least 98% crystallinity (e.g., about 2% amorphous form), at least 99% crystallinity (e.g., 1% amorphous form), and 100% crystallinity (e.g., 0% amorphous form).

[0124] 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 produce substantially the same results.

[0125] Example

[0126] The following further illustrates the present invention but does not limit its scope.

[0127] In these examples, X-ray diffraction (XRD) patterns of the as-synthesized and calcined materials were recorded in continuous mode on an X-ray powder diffractometer (Bruker DaVinci D8 Discovery instrument) using Cu Kα radiation, Bragg-Brentano geometry, and a Vantec 500 detector in the 2θ range of 2 to 50 degrees. The interplanar spacings, d-spacings, are calculated in angstroms, and the relative intensities of the lines, 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 position of the diffraction peak (expressed in 2θ) and the relative peak area intensity of the spectral line I / I(o) are determined using the MDIJade peak search algorithm, 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 lines, which can appear as split or partially split spectral lines under specific conditions such as differences in crystallization changes. Typically, crystallization changes can include slight changes in unit cell parameters and / or changes in crystal symmetry without changes in framework connectivity. These smaller effects, including changes in relative intensity, can also be the result of differences in cation content, framework composition, the nature and degree of pore filling, crystal size and shape, preferred orientation, and thermal and / or hydrothermal experience.

[0128] Scanning electron microscopy (SEM) images of the as-synthesized material were obtained on a Hitachi 4800 scanning electron microscope. SEM images are used to aid in the assessment of product purity. The presence of distinct crystal morphologies in the SEM images can indicate the presence of impurities in the form of other crystalline materials. This approximate analysis can be particularly useful in identifying relatively small amounts of crystalline impurities that cannot be identified in the product XRD pattern.

[0129] The total BET surface area (SBET) of the material was determined by the BET method as described in S. Brunauer et al. (1938) "Adsorption of Gases in Multimolecular Layers", J. Am. Chem. Soc., Vol. 60(2), pp. 309-319, which is incorporated herein by reference, using nitrogen adsorption-desorption at liquid nitrogen temperature. 外 ) was obtained by the t-plot method, and the micropore surface area (S micro) of the material was obtained by dividing the total BET surface area (S BET ) minus the external surface area (Souter).

[0130] The pore volume (V) of a material can be determined using methods known in the art. 微 ) and total pore volume (V 总 For example, the micropore volume 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. (1965), "Studies on Pore System in Catalysts: V. The t Method", J. Catal., Vol. 4(3), pp. 319-323, which describes micropore volume and total pore volume methods and is incorporated herein by reference.

[0131] The molar ratios and conditions used to synthesize Examples 2 to 14 and the resulting products are detailed below and summarized in Table 3.

[0132] Example 1a: 1-Methylimidazo[1,2-a]pyridine-1- Synthesis of cation (SDA-1)

[0133] 1-Methylimidazo[1,2-a]pyridine-1- Iodide: A mixture of 25 g (211.61 mmol) imidazo[1,2-a]pyridine and 69.08 g (486.71 mmol) methyl iodide in 265 mL acetonitrile was heated to 80°C for 10 hours. After 10 hours, thin layer chromatography showed remaining starting material. The reaction mixture was cooled to room temperature, and the acetonitrile was removed by rotary evaporation. The resulting yellow oil was triturated with 200 mL ethyl acetate, and the yellow solid was collected. 1 H-NMR showed the presence of the desired product and impurities. Impurities were removed by heating the yellow solid to 50°C in 200 mL of acetone and filtering off the remaining solid material. 1 H-NMR confirmed that the desired product was obtained cleanly.

[0134] 1-Methylimidazo[1,2-a]pyridine-1- Hydroxide: Use ion exchange resin IRN78OH hydroxide form (wherein the ratio of iodide ion:resin:water is 1:3.5:5) was used to exchange the iodide salt for the hydroxide form. The exchange was performed overnight at room temperature.

[0135] Example 1b: 1,2-Dimethylimidazo[1,2-a]pyridine-1- Synthesis of cation (SDA-2)

[0136] 1,2-Dimethylimidazo[1,2-a]pyridine-1- Iodide: A mixture of 26.52 g (200.65 mmol) 2-methylimidazo[1,2-a]pyridine and 29.90 g (210.68 mmol) methyl iodide in 250 mL acetonitrile was stirred at room temperature for 16 hours. The solid was filtered and rinsed with 200 mL ethyl acetate, air-dried for 30 minutes, and then 1 H-NMR. 1 H-NMR confirmed that the desired product was obtained cleanly.

[0137] 1,2-Dimethylimidazo[1,2-a]pyridine-1- Hydroxide: Use ion exchange resin IRN78OH hydroxide form (wherein the ratio of iodide ion:resin:water is 1:3.5:5) was used to exchange the iodide salt for the hydroxide form. The exchange was performed overnight at room temperature.

[0138] Example 1c: 1,5-Dimethyl-1H-pyrrolo[3,2-c]pyridine-5- Synthesis of cation (SDA-3)

[0139] 1,5-Dimethyl-1H-pyrrolo[3,2-c]pyridine-5- Iodide: 25.0 g (221.6 mmol) of 1H-pyrrolo[3,2-c]pyridine, 69.1 g (486.7 mmol) of iodomethane, and 13.1 g (232.8 mmol) of potassium hydroxide in 400 mL of acetonitrile were heated to 80°C for 6 hours. The acetonitrile was removed by rotary evaporation, and the residue was dissolved in 250 mL of chloroform. The potassium salt was removed by filtration, followed by removal of the chloroform by rotary evaporation. The residue was triturated with 350 mL of ethyl acetate, and the product precipitated as a tan solid. The solid was collected and air-dried for 30 minutes. 1 As confirmed by H-NMR, 55.5 g (96%) of 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- Iodide.

[0140] 1,5-Dimethyl-1H-pyrrolo[3,2-c]pyridine-5- Hydroxide: Use ion exchange resin IRN78OH hydroxide form (wherein the ratio of iodide ion:resin:water is 1:3.5:5) was used to exchange the iodide salt for the hydroxide form. The exchange was performed overnight at room temperature.

[0141] Example 1d: 1,6-dimethylimidazo[1,2-a]pyridine-1- Synthesis of cation (SDA-4)

[0142] 1,6-dimethylimidazo[1,2-a]pyridine-1- Iodide: To a stirred solution of 25 g (189.15 mmol) of 6-methylimidazo[1,2-a]pyridine in 236 mL of acetonitrile was added dropwise 53.7 g (378.3 mmol) of iodomethane at room temperature. The reaction was monitored by thin layer chromatography (TLC). When the starting 6-methylimidazo[1,2-a]pyridine disappeared, ether was added and a solid formed. The solid was collected by filtration, rinsed with 300 mL of ether and air-dried. 1 As confirmed by H-NMR, the reaction produced 439 g of the desired product.

[0143] 1,6-dimethylimidazo[1,2-a]pyridine-1- Hydroxide: Use ion exchange resin IRN78OH hydroxide form (wherein the ratio of iodide ion:resin:water is 1:3.5:5) was used to exchange the iodide salt for the hydroxide form. The exchange was performed overnight at room temperature.

[0144] Example 1e: 1,4-Dimethyl-1H-pyrrolo[3,2-b]pyridine-4- Synthesis of cation (SDA-5)

[0145] 1,4-Dimethyl-1H-pyrrolo[3,2-b]pyridine-4- Iodide: Heat 18.7 g of 4-azaindole, 52 g of iodomethane, and 10.0 g of potassium hydroxide in 200 mL of acetonitrile to 70°C overnight. Remove the acetonitrile via a rotary evaporator, and dissolve the residue in chloroform. Remove the potassium salt by filtration, followed by removal of the chloroform via a rotary evaporator. 1 H-NMR showed that the brown solid 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4- Iodide (or 1,4-dimethyl-4-azaindole iodide).

[0146] 1,4-Dimethyl-1H-pyrrolo[3,2-b]pyridine-4- Hydroxide: Use ion exchange resin IRN78OH hydroxide form (wherein the ratio of iodide ion:resin:water is 1:3.5:5) was used to exchange the iodide salt ion for its hydroxide form. The exchange was performed overnight at room temperature.

[0147] Example 2:SDA-2, USY zeolite, NaOH, Si / Al=15

[0148] In a PTFE-lined 10 mL steel Parr autoclave, the following were mixed together: 2.7 g 1,2-dimethylimidazo[1,2-a]pyridine-1- (SDA-2) hydroxide solution (5.9 wt%), 0.96 g of NaOH solution (4 wt%) and 0.46 g of ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (commercially available as CBV720 from Zeolyst) to produce a synthesis mixture with the following composition in molar ratios:

[0149] 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0150] The liner was then capped, sealed in a 10 mL Parr autoclave, and placed in a grill inside a convection oven. The reactor was heated at 160° C. for 1 week under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried in a ventilated drying oven at 90° C. The newly synthesized material was then calcined in a box furnace in air at a heating rate of 3° C. / minute to 580° C. The temperature was maintained at 580° C. for 8 hours, and then the box furnace was allowed to cool.

[0151] XRD analysis of the as-synthesized product and the calcined product showed that the material had a powder XRD pattern similar to that of the as-synthesized and calcined SSZ-48 molecular sieve in terms of 2θ degrees and d-spacing, respectively, but with different relative intensities (as shown, for example, in Tables I and II of U.S. Patent No. 6,080,382, which is incorporated herein by reference in its entirety). The new product was identified as EMM-74. Figure 1 and Figure 2 Shown are the powder XRD patterns of the as-synthesized and calcined EMM-74 materials of Example 2. Tables 4 and 5 below show a list of peaks and intensities for the as-synthesized and calcined EMM-74 materials of Example 2.

[0152] EMM-74 material is shown with dimensions of The SFE framework type with 12-ring pore channels (12MR).

[0153] The EMM-74 material has a uniform rod-like morphology with a particle diffusion length of about 300 nm, a diameter (or width or thickness) of about 50 nm, and an aspect ratio (l / d) of about 6. Figure 3 As shown, this figure shows the SEM image of the as-synthesized product of Example 2.

[0154] The micropore surface area (S) of the calcined EMM-74 material微 ) is 302m 2 / g, and the external surface area (Souter) is 53m 2 / g, and the total pore volume (Vtotal) is 0.31 cm 3 / g, micropore volume (V micro) is 0.12cm 3 / g. The adsorption capacities for n-hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and mesitylene were 73 mg / g, 67 mg / g, 57 mg / g, and 59 mg / g, respectively. These data indicate that a significant portion of the micropore volume of EMM-74 is available for these adsorbate molecules. The 12MR pore channels are clearly large enough to accommodate 1,3,5-trimethylbenzene (mesitylene), resulting in similar capacities for smaller adsorbates.

[0155] Example 3: SDA-2, USY zeolite, sodium aluminate, NaOH, Si / Al=16.5

[0156] This example was carried out under similar conditions to Example 2, but using ultrastable Y (USY) zeolite (commercially available as CBV760 from Zeolyst) with a Si / Al molar ratio of 30 and sodium aluminate (NaAlO2, 25 wt% Al2O3, 19.3 wt% Na2O) as Si and Al sources, resulting in the following composition in molar ratios:

[0157] 30H2O:1SiO2:0.03Al2O3:0.15QOH:0.15NaOH.

[0158] After heating at 160°C for 10 days, pure EMM-74 product was obtained as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2 as determined by SEM.

[0159] Example 4: SDA-2, USY zeolite, sodium aluminate, NaOH, Si / Al=25

[0160] This example was carried out under similar conditions to Example 3, but the synthesis mixture contained a lower amount of Al and a lower amount of NaOH, resulting in the following composition in molar ratios:

[0161] 30H2O:1SiO2:0.02Al2O3:0.15QOH:0.1NaOH.

[0162] After heating at 160°C for 10 days, pure EMM-74 product was obtained as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2 as determined by SEM.

[0163] Example 5: SDA-2, colloidal silica, sodium aluminate, NaOH, Si / Al=15

[0164] This example was carried out under similar conditions to Example 3, but using Ludox HS40 (40 wt% colloidal silica suspension) as the Si source and sodium aluminate (NaAlO2, 25 wt% Al2O3, 19.3 wt% Na2O) as the Al source, to obtain a synthetic mixture having the following composition in molar ratio:

[0165] 33H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0166] After heating at 160° C. for 3 weeks, an EMM-74 product containing a small amount of FER material was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2, as determined by SEM.

[0167] Example 6: SDA-2, colloidal silica, sodium aluminate, NaOH, Si / Al=22.5

[0168] This example was carried out under similar conditions to Example 5, but the synthesis mixture contained lower amounts of Al and NaOH, resulting in a synthesis mixture having the following composition in molar ratios:

[0169] 33H2O:1SiO2:0.022Al2O3:0.15QOH:0.10NaOH.

[0170] After heating at 160° C. for 3 weeks, an EMM-74 product containing a small amount of amorphous phase material was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2, as determined by SEM.

[0171] Example 7: SDA-2, USY zeolite, KOH, Si / Al=15

[0172] This example was carried out under similar conditions to Example 2, but KOH (20%) was used instead of NaOH, and the synthesis mixture also contained a smaller amount of water, resulting in a synthesis mixture having the following composition in terms of molar ratio:

[0173] 22H2O:1SiO2:0.033Al2O3:0.15QOH:0.15KOH.

[0174] After heating at 160°C for 1 week, pure EMM-74 product was obtained as identified by its XRD pattern.

[0175] The EMM-74 material of Example 7 has a uniform rod-like morphology, wherein the particle diffusion length is about 50 to 200 nm, the diameter (or width or thickness) is about 20 to 50 nm, and the aspect ratio (l / d) is about 2 to 8, as shown in FIG. Figure 4 As shown, this figure shows the SEM image of the as-synthesized product of Example 7.

[0176] Example 8: SDA-2, USY zeolite, KOH, Si / Al=30

[0177] This example was carried out under similar conditions to Example 7, but using ultrastable Y (USY) zeolite (commercially available from Zeolyst as CBV760) with a Si / Al molar ratio of 30 as the Si and Al sources, and the synthesis mixture also contained a higher amount of water and a lower amount of KOH, resulting in the following composition in molar ratios:

[0178] 30H2O:1SiO2:0.017Al2O3:0.15QOH:0.1KOH.

[0179] After heating at 160°C for 2 weeks, pure EMM-74 product was obtained as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2 as determined by SEM.

[0180] Example 9: SDA-2, USY zeolite, KOH, Si / Al=40

[0181] This example was carried out under similar conditions to Example 8, but the synthesis mixture contained a lower amount of Al, using ultrastable Y (USY) zeolite (commercially available as CBV780 from Zeolyst) with a Si / Al molar ratio of 40 as the Si and Al source, resulting in the following composition in molar ratios:

[0182] 30H2O:1SiO2:0.0125Al2O3:0.15QOH:0.1KOH.

[0183] After heating at 160° C. for 2 weeks, an EMM-74 product containing a small amount of quartz was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2, as determined by SEM.

[0184] Example 10: SDA-2, TEOS, aluminum hydroxide, HF, Si / Al=25

[0185] At room temperature, 1.43 g of tetraethyl orthosilicate (TEOS, >99 wt%) and 0.026 g of aluminum hydroxide (Sigma, 54 wt% Al2O3) were mixed with 9.6 g of 1,2-dimethylimidazo[1,2-a]pyridine-1- The mixture was then heated at about 50°C to remove ethanol and water. Subsequently, 0.14 HF (48 wt% solution) was added to the mixture, resulting in a synthetic mixture having the following composition in molar ratio:

[0186] 7.5H2O:1SiO2:0.02Al2O3:0.5QOH:0.5HF.

[0187] The resulting thick paste was homogenized by hand and transferred to the PTFE liner of a 10 mL steel Parr autoclave. The reactor was heated at 160° C. for 3 weeks under tumbling conditions (approximately 40 rpm). The product was separated by centrifugation, washed three times with distilled water (100 mL), and dried in a ventilated drying oven at 90° C. The newly synthesized material was then calcined to 580° C. in air at a heating rate of 3° C. / min in a box furnace. The temperature was maintained at 580° C. for 8 hours, and the box furnace was then allowed to cool.

[0188] XRD analysis of the as-synthesized product showed that the material was pure EMM-74 product. As determined by SEM, the EMM-74 product had a rod-like morphology similar to that of the product of Example 2.

[0189] Example 11: SDA-2, TEOS, aluminum hydroxide, HF, Si / Al=50

[0190] This example was carried out under similar conditions to Example 10, but the synthesis mixture contained a lower amount of Al and a higher amount of water, resulting in the following composition in molar ratios:

[0191] 15H2O:1SiO2:0.01Al2O3:0.5QOH:0.5HF.

[0192] After heating at 160° C. for 3 weeks, an EMM-74 product containing a small amount of unidentified impurities was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2, as determined by SEM.

[0193] Example 12: SDA-1, TEOS, Al hydroxide, HF, Si / Al=50

[0194] This example was carried out under the same conditions as Example 11, but using 1-methylimidazo[1,2-a]pyridine-1- (SDA-1) hydroxide instead of SDA-2 hydroxide. The synthesis mixture has the following composition in molar ratio:

[0195] 15H2O:1SiO2:0.01Al2O3:0.5QOH:0.5HF.

[0196] After heating at 160°C for 10 days, pure EMM-74 product was obtained as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2 as determined by SEM.

[0197] Example 13: SDA-4, USY zeolite, NaOH, Si / Al=15

[0198] Similar to the procedure of Example 2, the following materials were mixed together in a 10 mL steel Parr autoclave lined with PTFE: 1.41 g 1,6-dimethylimidazo[1,2-a]pyridine-1- (SDA-4) hydroxide solution (15 wt %), 0.51 g NaOH solution (10 wt %), 2.9 g deionized water and 0.61 g ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (commercially available from Zeolyst as CBV720) to produce a synthesis mixture with the following composition in molar ratios:

[0199] 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0200] The liner was then capped, sealed in a 10 mL Parr autoclave, and placed in a rack inside a convection oven under tumbling conditions (approximately 30 rpm). After heating at 160° C. for 20 days, a pure EMM-74 product was obtained, as identified by its XRD pattern. As determined by SEM, the EMM-74 product had a rod-like morphology similar to that of the product of Example 2.

[0201] Example 14: SDA-3, USY zeolite, NaOH, Si / Al=15

[0202] Similar to the procedure of Example 2, the following materials were mixed together in a 10 mL steel Parr autoclave lined with PTFE: 3.8 g of 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- (SDA-3) hydroxide solution (5.5 wt %), 0.51 g of NaOH solution (10 wt %) and 0.61 g of ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (commercially available as CBV720 from Zeolyst) to produce a synthesis mixture with the following composition in molar ratios:

[0203] 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0204] The liner was then capped, sealed in a 10 mL Parr autoclave, and placed in a grill inside a convection oven. The reactor was heated at 160° C. for 10 days under a tumbling condition (approximately 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried in a ventilated drying oven at 90° C. The newly synthesized material was then calcined in a box furnace in air at a heating rate of 3° C. / minute to 580° C. The temperature was maintained at 580° C. for 8 hours, and then the box furnace was allowed to cool.

[0205] XRD analysis of the as-synthesized product showed that the material was pure EMM-74 product. Figure 5 As shown, the figure shows an SEM image of the as-synthesized product of Example 14. The EMM-74 aluminosilicate of Example 14 prepared using SDA-3 has a uniform plate-like morphology with a length of about 100 nm to 150 nm, a width of about 50 nm to 100 nm, and a thickness of about 20 nm to 30 nm.

[0206] Example 15: SDA-3, USY zeolite, NaOH, Si / Al=15

[0207] Example 14 was repeated with a slightly smaller amount of water to obtain a synthetic mixture having the following composition in molar ratios:

[0208] 27H2O:1SiO2:0.033Al2O3:0.15QOH:0.15NaOH.

[0209] After heating at 170°C for 10 days, pure EMM-74 product was obtained as identified by its XRD pattern. The EMM-74 product had a plate-like morphology similar to that of the product of Example 14 as determined by SEM.

[0210] Example 16: SDA-3, colloidal silica, aluminum hydroxide, NaOH, Si / Al=20

[0211] This example was carried out under similar conditions to Example 14, but using Ludox AS40 (40 wt% colloidal silica suspension) as the Si source and aluminum hydroxide (Sigma, 54 wt% Al2O3) as the Al source, to obtain a synthetic mixture having the following composition in molar ratio:

[0212] 30H2O:1SiO2:0.025Al2O3:0.15QOH:0.15NaOH.

[0213] After heating at 160° C. for 10 days, an EMM-74 product containing a small amount of FER material was obtained, as identified by its XRD pattern. The EMM-74 product had a plate-like morphology similar to that of the product of Example 14, as determined by SEM.

[0214] Example 17: SDA-2, colloidal silica, boric acid, Si / B=10

[0215] In a PTFE-lined 10 mL steel Parr autoclave, the following were mixed together: 8.6 g 1,2-dimethylimidazo[1,2-a]pyridine-1- (SDA-2) hydroxide solution (5.9 wt %), 1.16 g Ludox HS40 (40 wt % colloidal silica suspension) and 1.23 g boric acid (3.87 wt % H3BO3 solution) were added, and the water was allowed to vaporize to produce a synthetic mixture having the following composition in molar ratio:

[0216] 10H2O:1SiO2:0.05B2O3:0.4QOH.

[0217] The liner was then capped, sealed in a 10 mL Parr autoclave, and placed in a grill inside a convection oven. The reactor was heated at 160° C. for 3 weeks under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried in a ventilated drying oven at 90° C. The newly synthesized material was then calcined to 580° C. in air at a heating rate of 3° C. / minute in a box furnace. The temperature was maintained at 580° C. for 8 hours, and the box furnace was then allowed to cool.

[0218] Figure 6 and Figure 7 Powder XRD patterns for the as-synthesized material and the calcined material corresponding to the pure EMM-74 product are shown. Tables 6 and 7 below show a list of peaks and intensities for the as-synthesized and calcined EMM-74 materials of Example 17.

[0219] like Figure 8As shown, the figure shows an SEM image of the as-synthesized product of Example 17. The EMM-74 borosilicate of Example 17 has a uniform rod-like morphology similar to the product of Example 2, wherein the particle diffusion length is about 300 nm and the diameter (or width or thickness) is about 50 nm.

[0220] Example 18: SDA-2, Y-type zeolite, boric acid, NaOH, Si / B = 16.5, Si / Al = 50

[0221] This example was carried out under similar conditions to Example 3, but using Y-type zeolite (commercially available from Tosoh as HSZ-385HUA) with a Si / Al molar ratio of 50 as Si and Al sources, and adding boric acid as B source (3.87 wt% H3BO3 solution), resulting in the following composition in molar ratio:

[0222] 30H2O:1SiO2:0.03B2O3:0.01Al2O3:0.15QOH:0.15NaOH.

[0223] After heating at 160° C. for 10 days, a pure aluminoborosilicate EMM-74 product was obtained, as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2, as determined by SEM.

[0224] Example 19: SDA-2, Y-type zeolite, boric acid, NaOH, Si / B = 10, Si / Al = 250

[0225] This example was carried out under similar conditions to Example 18, but the synthesis mixture contained a smaller amount of water, a larger amount of boron and a smaller amount of aluminum, using Y-type zeolite (commercially available from Tosoh as HSZ-390HUA) with a Si / Al molar ratio of 250 as the Si and Al sources, resulting in the following composition in molar ratios:

[0226] 25H2O:1SiO2:0.05B2O3:0.002Al2O3:0.15QOH:0.15NaOH.

[0227] After heating at 160°C for 6 days, pure EMM-74 product was obtained as identified by its XRD pattern. The EMM-74 product had a rod-like morphology similar to that of the product of Example 2 as determined by SEM.

[0228] Example 20: SDA-5, USY zeolite, KOH, Si / Al=15

[0229] In a PTFE-lined 23 mL steel Parr autoclave, the following materials were mixed together: 3.1 g of 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4- (SDA-5) hydroxide solution (9.4 wt %), 0.36 g of KOH solution (20 wt %), 2.25 g of deionized water and 0.61 g of ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (commercially available as CBV720 from Zeolyst) to produce a synthesis mixture with the following composition in molar ratios:

[0230] 30H2O:1SiO2:0.033Al2O3:0.15QOH:0.15KOH.

[0231] The liner was then capped, sealed in a 23 mL Parr autoclave, and placed in a rack inside a convection oven. The reactor was heated at 160° C. under tumbling conditions (approximately 30 rpm) for 8 days. The product was isolated by filtration, rinsed with deionized water, and dried.

[0232] XRD analysis of the as-synthesized product showed that the material was pure EMM-74 product.

[0233] Table 3

[0234]

[0235] *SDA-1=1-methylimidazo[1,2-a]pyridine-1- cation

[0236] SDA-2=1,2-dimethylimidazo[1,2-a]pyridine-1- cation

[0237] SDA-3=1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- cation

[0238] SDA-4=1,6-dimethylimidazo[1,2-a]pyridine-1- Cationic SDA-5=1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4- cation

[0239] Table 4

[0240]

[0241] Table 5

[0242]

[0243]

[0244] Table 6

[0245]

[0246] Table 7

[0247]

[0248] Although the present invention has been described and exemplified with reference to specific embodiments, it will be understood by those skilled in the art that the present invention is susceptible to many different variations, modifications, and variations not specifically described herein. It will also be clear to 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. In addition, all numerical values within the detailed description herein are modified by the indicated value "about," and take into account experimental errors and variations expected by those skilled in the art.

[0249] Where the foregoing description mentions wholes or elements that have known, obvious or foreseeable equivalents, such equivalents are incorporated herein as if set forth individually. Reference should be made to the claims to determine the true scope of the invention, which should be deemed to encompass any such equivalents. The reader should also understand that wholes or features of the invention that are 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 wholes or features, while beneficial in some embodiments of the invention, may be undesirable in other embodiments and, therefore, may not exist.

[0250] Additionally or alternatively, the present invention relates to:

[0251] Embodiment 1: A molecular sieve having an X-ray diffraction pattern comprising the peaks in Table 1 in its calcined form.

[0252] Embodiment 2: The molecular sieve according to embodiment 1, wherein the molecular sieve has a molecular formula of Formula V:

[0253] (m) X2O3:YO2 (Formula V),

[0254] Wherein 0≤m≤0.1, X is a trivalent element, and Y is a tetravalent element.

[0255] Embodiment 3: The molecular sieve according to embodiment 2, wherein X comprises one or more of aluminum, boron, iron and gallium, preferably X comprises or is aluminum and / or boron.

[0256] Embodiment 4: The molecular sieve according to Embodiment 2 or 3, wherein Y comprises one or more of silicon, titanium, zirconium, tin, and germanium, preferably Y comprises silicon and / or germanium or is silicon and / or germanium, more preferably comprises silicon or is silicon.

[0257] Embodiment 5: A molecular sieve, which in its as-synthesized form has an X-ray diffraction pattern comprising the peaks in Table 2.

[0258] Embodiment 6: The molecular sieve according to Embodiment 5, which has the molecular formula of Formula V:

[0259] (q)Q:(m)X2O3:YO2 (Formula V),

[0260] where 0 < q ≤ 0.7, 0 ≤ m ≤ 0.1, X is a trivalent element, Y is a tetravalent element, and Q comprises at least one cation selected from the 1-methylimidazo[1,2-a]pyridin-1- cation of Formula I, the 1,2-dimethylimidazo[1,2-a]pyridin-1- cation of Formula II, the 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridin-5- cation of Formula III, the 1,6-dimethylimidazo[1,2-a]pyridin-1- cation of Formula IV, and the 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridin-4-

[0261]

[0262] Embodiment 7: The molecular sieve according to Embodiment 6, wherein X comprises one or more of aluminum, boron, iron, and gallium, preferably X comprises aluminum and / or boron or is aluminum and / or boron.

[0263] Embodiment 8: The molecular sieve according to Embodiment 6 or 7, wherein Y comprises one or more of silicon, titanium, zirconium, tin, and germanium, preferably Y comprises silicon and / or germanium or is silicon and / or germanium, more preferably comprises silicon or is silicon.

[0264] Embodiment 9: The molecular sieve according to any one of the foregoing embodiments, wherein at least a part of the molecular sieve crystals has a rod-like morphology.

[0265] Embodiment 10: The molecular sieve according to Embodiment 9, the length of the molecular sieve is from 30 nm to 10 mm, preferably from 100 nm to 1 mm, more preferably from 100 nm to 500 nm, and the aspect ratio of the molecular sieve is greater than 1 to 10, especially 2 to 8.

[0266] Embodiment 11: The molecular sieve of any one of Embodiments 1 to 8, wherein at least a portion of the molecular sieve crystals have a plate-like morphology.

[0267] Embodiment 12: According to the molecular sieve described in embodiment 11, the length of the molecular sieve is 75nm to 1mm, preferably 75nm to 500nm, more preferably 100nm to 300nm, and the thickness of the molecular sieve is 5nm to 60nm, especially 10nm to 50nm, more especially 20 to 30nm.

[0268] Embodiment 13: The molecular sieve according to any one of the preceding embodiments, wherein the molecular sieve is a silicate, an aluminosilicate, a borosilicate or an aluminoborosilicate, and the Si / X molar ratio of the molecular sieve is 5 to 300 (if Al and / or B are present), preferably 10 to 100, and more preferably 15 to 75.

[0269] Embodiment 14: A method of making the molecular sieve of any of the preceding embodiments, the method comprising:

[0270] (a) preparing a synthesis mixture comprising water, a source of a tetravalent element (Y) oxide, a source of a trivalent element (X) oxide, a structure directing agent (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F) and optionally a source of an alkali metal and / or alkaline earth metal element (M),

[0271] wherein the structure directing agent (Q) comprises at least one cation selected from 1-methylimidazo[1,2-a]pyridine-1- Cation, 1,2-dimethylimidazo[1,2-a]pyridine-1- cation, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- cation, 1,6-dimethylimidazo[1,2-a]pyridine-1- cation and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4-

[0272]

[0273] (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100° C. to 200° C. for a time sufficient to form crystals of the molecular sieve;

[0274] (c) recovering at least a portion of the molecular sieve from step (b); and

[0275] (d) optionally treating the molecular sieve recovered in step (c) to remove at least a portion of the structure directing agent (Q).

[0276] Embodiment 15: The method according to embodiment 14, 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.

[0277] Embodiment 16: A method according to embodiment 14 or 15, wherein the tetravalent element (Y) is selected from silicon, titanium, zirconium, tin, germanium and mixtures thereof, preferably wherein the tetravalent element (Y) comprises silicon and / or germanium, more preferably wherein the tetravalent element (Y) is silicon and / or germanium, most preferably silicon.

[0278] Embodiment 17: A method according to any one of embodiments 14 to 16, wherein the trivalent element (X) is selected from aluminum, boron, iron, gallium and mixtures thereof, preferably 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.

[0279] Embodiment 18: The method of any one of Embodiments 14 to 17, wherein the synthesis mixture has the following composition in molar ratio:

[0280]

[0281] Embodiment 19: A method of converting an organic compound to a conversion product, the method comprising contacting the organic compound with the molecular sieve of any one of Embodiments 1 to 13.

Claims

1. A molecular sieve having, in its calcined form, an X-ray diffraction pattern comprising the peaks in Table 1 below: Table 1 2. The molecular sieve according to claim 1, wherein the molecular sieve has a molecular formula of Formula V: (m) X2O3:YO2 (Formula V), wherein 0≤m≤0.1, X is a trivalent element, and Y is a tetravalent element; in particular, wherein X comprises one or more of aluminum, boron, iron and gallium, preferably X comprises aluminum and / or boron or is aluminum and / or boron, and Y comprises one or more of silicon, titanium, zirconium, tin and germanium, preferably Y comprises silicon and / or germanium or is silicon and / or germanium, more preferably comprises silicon or is silicon.

3. A molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern comprising the peaks in Table 2 below: Table 2 4. The molecular sieve according to claim 3, wherein the molecular sieve has the molecular formula VI: (q)Q:(m)X2O3:YO2 (Formula VI), where 0 < q ≤ 0.7, 0 ≤ m ≤ 0.1, X is a trivalent element, Y is a tetravalent element, and Q contains at least one cation selected from: 1-methylimidazo[1,2-a]pyridin-1- cation of formula I, 1,2-dimethylimidazo[1,2-a]pyridin-1- cation of formula II, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridin-5- cation of formula III, 1,6-dimethylimidazo[1,2-a]pyridin-1- cation of formula IV, and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridin-4- In particular, X comprises one or more of aluminum, boron, iron and gallium, preferably X comprises aluminum and / or boron or is aluminum and / or boron, and Y comprises one or more of silicon, titanium, zirconium, tin and germanium, preferably Y comprises silicon and / or germanium or is silicon and / or germanium, more preferably comprises silicon or is silicon.

5. The molecular sieve according to any one of claims 1 to 4, wherein at least a portion of the molecular sieve crystals have a rod-like morphology. The molecular sieve according to claim 5 , wherein the length of the molecular sieve is 30 nm to 10 mm, preferably 100 nm to 1 mm, more preferably 100 nm to 500 nm, and the aspect ratio of the molecular sieve is greater than 1 to 10, particularly 2 to 8.

7. The molecular sieve according to any one of claims 1 to 4, 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 a silicate, an aluminosilicate, a borosilicate or an aluminoborosilicate, and has a Si / X molar ratio of 5 to 300 (if Al and / or B are present), preferably 10 to 100, more preferably 15 to 75.

9. A method for producing the molecular sieve according to any one of claims 1 to 8, the method comprising: (a) preparing a synthesis mixture comprising water, a source of a tetravalent element (Y) oxide, a source of a trivalent element (X) oxide, a structure directing agent (Q), optionally a source of hydroxide ions (OH), optionally a source of fluoride ions (F) and optionally a source of an alkali metal and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 1-methylimidazo[1,2-a]pyridine-1- Cation, 1,2-dimethylimidazo[1,2-a]pyridine-1- cation, 1,5-dimethyl-1H-pyrrolo[3,2-c]pyridine-5- cation, 1,6-dimethylimidazo[1,2-a]pyridine-1- cation and 1,4-dimethyl-1H-pyrrolo[3,2-b]pyridine-4- (b) heating the synthesis mixture under crystallization conditions comprising a temperature of 100° C. to 200° C. for a time sufficient to form crystals of the 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 according to 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 according to claim 9 or 10, wherein the tetravalent element (Y) is selected from silicon, titanium, zirconium, tin, germanium and mixtures thereof, preferably wherein the tetravalent element (Y) comprises silicon and / or germanium, more preferably wherein the tetravalent element (Y) is silicon and / or germanium, most preferably silicon.

12. The method according to any one of claims 9 to 11, wherein the trivalent element (X) is selected from the group consisting of aluminum, boron, iron, gallium and mixtures thereof, preferably 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.

13. The process according to any one of claims 9 to 12, wherein the synthesis mixture has the following composition in molar ratio:

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

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