Intramolecular π-stacking structure directing agent and molecular sieve synthesized therefrom

Abstract

The method for producing a molecular sieve may include: causing a source selected from a tetrahedral element source to react with a source selected from an Ar + ‑L‑Ar, Ar + ‑L‑Ar‑L‑Ar + ,Ar + ‑L‑Ar‑L‑NR3 + andArAr + ‑L‑Ar + Ar structure directing agent (SDA) in the presence of to produce a molecular sieve, wherein Ar + is a cationic aromatic ring containing N, Ar is an uncharged aromatic ring, L is a methylene chain of 3-6 carbon atoms, NR3 + is a quaternary ammonium, and ArAr + and Ar + Ar is a fused aromatic ring structure comprising both a N-containing cationic portion and an uncharged portion.

Description

Technical Field

[0001] The present disclosure relates to structure directing agents that are capable of assuming bulky conformations due to intramolecular π-stacking. The present disclosure also relates to molecular sieves produced by such structure directing agents, characterized by large cages, large cavities, and / or large pores. Background Art

[0002] Molecular sieves have a wide range of industrial applications, including catalysis, ion exchange, gas adsorption, and molecular separation. Many of the properties and resulting applications of molecular sieves derive from the size and shape of the pore structure. There remains a need for all-silica, aluminosilicate, or borosilicate molecular sieves with large cages, large cavities, or large pores. Such molecular sieves are often obtained by using bulky quaternary ammonium or The molecules were prepared as structure directing agents (SDAs).

[0003] For example, Lee and Zones used compound A (wherein R1 is preferably H, R2 and R3 are preferably CH3, and R4 is preferably CH3CH2) to prepare SSZ-50, which is an aluminosilicate with an RTH topological structure (Lee, GS and Zones, SI, Polymethylated [4.1.1] octanes leading to molecular sieve SSZ-50, J. Solid State Chem., 167, 289-298 (2002)).

[0004]

[0005] The RTH framework has a large cage, which has two vertical 8-ring channels intersecting at a large cavity. The bulkiness of the molecule provides a good fit in the large cage of the framework. The RTH type molecular sieve can also be made into borosilicates (Wagner, P., Nakagawa, Y., Lee, GS, Davis, ME, Elomari, S., Medrud, RC and Zones, SIJ Am. Chem. Soc., 122, 263-273 (2000) and Vortmann, S., Marler, B., Gies, H. and Daniels, P. Microporous Materials, 4, 111-121 (1995)) with many SDAs. However, in this regard, compound A is the only quaternary ammonium molecule that causes the RTH framework structure of aluminosilicate form.

[0006] Compound A requires a 7-8 step synthesis using lithium aluminum hydride reduction. The expense and risk of preparing Compound A makes it difficult to prepare, especially on the large scale required for commercial implementation of the above RTH topology molecular sieves in aluminosilicate form.

[0007] There is a related molecular sieve structure, ITQ-3 (Ite, Camblor, MA, Corma, A., Lightfoot, P., Villaescusa, LA and Wright, PA Angew. Chem. Int. Ed., 36, 2659-2661 (1997)), which has the same layers present in the RTH structure, except that the layers are related by mirror symmetry rather than by inversion centers. The cage sizes of RTH and ITE are similar but the shapes are different. ITQ-3 is reported to be prepared in fluoride media as all-silica and aluminosilicate using amine precursors that are not readily available. The same SDA molecule used to produce the ITE structure is reported to be used to prepare the SSZ-36 structure as an aluminosilicate in a hydroxide medium (J. Am. Chem. Soc., 122, 263-273 (2000)). Another aluminosilicate ITE type molecular sieve using compound B as SDA was reported by Mulhouse's workers (Valtchev, V., Paillaud, JL, Lefebvre, T., Lenouen, D. and Kessler, H. Microporous Mesoporous Mat., 38, 177-185 (2000)). Again, this is a polycyclic molecule and its preparation requires a multi-step procedure.

[0008]

[0009] Another cage-based molecular sieve with a macroporous structure is ITQ-52 (IFW, Simancas, R., Jorda, JL, Rey, F., Corma, A., Cantin, A., Peral, I. and Popescu, CJ Am. Chem. Soc., 136, 333 2-3345 (2014)) and isostructural SSZ-87 (Smeets, S., McCusker, LB, Baerlocher, Ch.., Xie, D., Chen, C.-Y. and Zones, SIJ Am. Chem. Soc., 137, 2015-2020 (2015)). ITQ-52 is prepared from compound C derived from an aminophosphine intermediate. Isostructural SSZ-87 is prepared from compound D, which is prepared via a multi-step sequence requiring lithium aluminum hydride reduction.

[0010]

[0011] Compounds AD are all relatively bulky and can be used to prepare molecular sieves with large cages, large cavities or large pores. However, these molecules are difficult to prepare or require expensive intermediates.

[0012] Other syntheses using SDAs that are difficult to prepare or require expensive intermediates are described in the literature, for example, ITQ-29: Supramolecular self-assembled molecules as organic direction agent for synthesis of zeolites, Nature, 431, 287-290 (2004); ITQ-27: P-derived organic cations as structure directing agents: Synthesis of a High-Silica Zeolite (ITQ-27) with a Two-dimensional 12-Ring Channel System, J. Am. Chem. Soc. 128, 8862-8867 (2006); CIT-13 and NUD-2: Synthesis and Characterization of CIT-13, a Germanosilicate Molecular Sieve with Extra-Large Pore Openings, Chem. Mater., 28, 6250-6259 (2016) and A stable extra-large-pore zeolite with intersecting 14-and 10-membered-ring channels, Chem. Eur. J., 22, 146 7-14372 (2016); and STA-6: Synthesis of a novel microporousmagnesioaluminophosphate, STA-6, containing an unbound azamacrocycle, J. Chem. Soc., Dalton Trans., 3909-3911 (1999). Summary of the invention SUMMARY OF THE INVENTION

[0014] The present disclosure relates to structure directing agents capable of assuming bulky conformations due to intramolecular π-stacking. The present disclosure also relates to molecular sieves produced by such structure directing agents, characterized by large cages, large cavities, and / or large or ultra-large pores (12 rings and 14 or more rings, respectively).

[0015] The method of the present disclosure may include: causing a source selected from a tetrahedral element source to be in a state selected from Ar + -L-Ar, Ar + -L-Ar-L-Ar + and Ar + -L-Ar-L-NR3 + to produce a molecular sieve in the presence of a structure directing agent (SDA) wherein Ar + refers to a cationic aromatic ring containing N, Ar refers to an uncharged aromatic ring, L is a methylene chain of 3-6 carbon atoms, NR3 + It refers to quaternary ammonium.

[0016] The method of the present disclosure may include: causing a source selected from a tetrahedral element source to react in an ArAr + -L-Ar + Ar is reacted in the presence of a structure directing agent (SDA) to produce a molecular sieve, wherein L is a methylene chain of 3 to 6 carbon atoms, and ArAr + and Ar + Ar is a fused aromatic ring structure comprising both a N-containing cationic portion and an uncharged portion.

[0017] The composition of the present disclosure may include an aluminosilicate molecular sieve or an aluminoborosilicate molecular sieve having a RHO framework having a Si to Al ratio of greater than or equal to about 8.

[0018] The composition of the present disclosure may include: a borosilicate molecular sieve having an RHO framework. The borosilicate molecular sieve may have a Si to B ratio of about 1 to about 25 (or about 8 to about 25).

[0019] The composition of the present disclosure may include: a silica molecular sieve having an IFW framework.

[0020] The composition of the present disclosure may include: an aluminosilicate molecular sieve having an IFW framework.

[0021] The composition of the present disclosure may include: a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve, or a germanosilicate molecular sieve having an ITH / RTH intergrowth framework.

[0022] The composition of the present disclosure may include: a silica molecular sieve or a borosilicate molecular sieve having a *CTH framework, which may not contain Ge.

[0023] The composition of the present disclosure may include: a silicoaluminophosphate molecular sieve having a SAS framework. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A diagram showing a non-limiting example of a proposed π-stacking conformational structure.

[0026] Figure 2 The molecular model of the following compound E (R1 and R2 are methyl groups, R3-R 10 Yes H).

[0027] Figure 3 is a scanning electron microscope (SEM) micrograph of the borosilicate Rho molecular sieve of the present invention.

[0028] Figures 4A-4D is a SEM micrograph of the borosilicate Rho molecular sieve of the present invention.

[0029] Figure 5 The X-ray diffraction patterns of the original borosilicate Rho molecular sieve and the calcined borosilicate Rho molecular sieve are shown in FIG.

[0030] Fig. 6A and 6B is a SEM micrograph of the borosilicate Rho molecular sieve of the present invention.

[0031] Figure 7 is a SEM micrograph of the borosilicate Rho molecular sieve of the present invention.

[0032] Fig. 8A and 8B is a SEM micrograph of the borosilicate Rho molecular sieve of the present invention.

[0033] Fig. 9 These are the X-ray diffraction (XRD) patterns of aluminosilicate Rth molecular sieve (upper figure) and borosilicate Rth molecular sieve (lower figure).

[0034] Fig.10 is the XRD pattern of borosilicate with pure RTH-type phase.

[0035] Fig.11A and 11B yes Fig.10 SEM micrograph of a borosilicate with a pure RTH-type phase.

[0036] Fig.12 is the XRD pattern of aluminosilicate with pure ITE type phase.

[0037] Fig.13A and 13B yes Fig.12 SEM micrograph of an aluminosilicate with a pure ITE-type phase.

[0038] Fig.14It is a drawing of XRD patterns of ITE / RTH type phase molecular sieve compared with pure ITE type phase molecular sieve and pure RTH type phase molecular sieve.

[0039] Fig.15A and 15B is a SEM micrograph of an IFW-type phase aluminoborosilicate without any phyllosilicate or quartz impurities.

[0040] Fig.16 is an XRD pattern depiction of aluminoborosilicate with a pure IFW-type phase.

[0041] Fig.17A and 17B The XRD patterns of borosilicate IFW-type molecular sieves (above) and aluminosilicate IFW-type molecular sieves (below) are shown. Fig. 17B yes Fig.17A The enlarged part. DETAILED DESCRIPTION OF THE INVENTION

[0043] The present disclosure relates to the synthesis of molecular sieves using organic structure directing agents (SDAs) capable of intramolecular π-stacking. Intramolecular stacking is generally achieved by separating the N-containing cationic aromatic portion of the molecule from the uncharged aromatic portion of the molecule via an alkyl linker. Without wishing to be bound by theory, it is believed that the alkyl linker assumes a conformation in which the N-containing cationic aromatic portion and the uncharged aromatic portion of the SDA sandwich the π-stacked structure. Figure 1 A diagram of a non-limiting example of a proposed π-stacked conformational structure 100 is shown, wherein circles 102 and 104 extending into and out of the plane of the paper are used to visually represent the N-containing cationic aromatic portion of the SDA and the uncharged aromatic portion of the SDA, respectively. Line 106 represents a linker. Depending on the length of the linker and the overlap of the N-containing cationic aromatic portion and the uncharged aromatic portion of the SDA, the linker can be completely within the plane of the paper or within and outside the plane of the paper. Because the SDA extends into and out of the plane of the paper, the π-stacked conformational structure 100 has a significant three-dimensional dimension that provides significant volume to the SDA, particularly if the N-containing cationic aromatic and / or uncharged aromatic portion of the SDA has functional groups (e.g., alkyl groups) extending therefrom. More specifically, Figure 2 The molecular model of the following compound E (R1 and R2 are methyl groups, R3-R 10 is H), where the dotted elements are nitrogen, the white elements are carbon, and the grey elements are grey.

[0044] As shown herein, SDA with this π-stacking conformation ability can be used to synthesize molecular sieves with large cages, large cavities and / or large or ultra-large pores. The π-stacking conformation is indirectly inferred by the observed size of the cage, cavity or hole in which the SDA molecule is enclosed. The π-stacking conformation has been independently observed and described in "Intramolecular cation-P interactions control the conformation of nonrestricted (phenylalkyl) pyridines", Chem. Commun., 2008, 1082-1084. If linear conformers rather than intramolecular stacked conformers are the main ones for these molecules, ZSM-12 (MTW) ​​or other one-dimensional frameworks will be expected to be common products. This one-dimensional framework is rarely observed in the synthesis described herein.

[0045] In addition, the SDA described herein can be used to form different molecular sieve frameworks. As shown in the examples, the resulting framework is affected by the position where additional volume is added to the SDA via derivatives on the N-containing cationic aromatic ring. For example, Example 12 and Example 13 were each performed with different SDA embodiments of Compound E. Compared to the SDA of Example 12, the SDA of Example 13 has an additional methyl group. Under a similar range of inorganic conditions, Example 12 primarily produces an RTH framework, while Example 13 primarily produces an ITE framework. The frameworks are very similar in structure, but the RTH framework has inversion centrosymmetry, while the ITE framework has mirror symmetry.

[0046] Organic structure-directing agents capable of intramolecular π-stacking

[0047] The SDAs described herein that are capable of intramolecular π-stacking have one of the following four general structures: (a) Ar + -L-Ar,(b)Ar + -L-Ar-L-Ar + ,(c)Ar + -L-Ar-L-NR3 + and (d)ArAr + -L-Ar + Ar, of which Ar + refers to a cationic aromatic ring containing N, Ar refers to an uncharged aromatic ring, L refers to a linking group, NR3 + refers to quaternary ammonium, ArAr + and Ar + Ar refers to a fused aromatic ring structure comprising both a N-containing cationic moiety and an uncharged moiety, wherein the -linkage to L indicates that L is bonded to the moiety on the fused aromatic ring structure.

[0048] Without wishing to be bound by theory, it is believed that Ar (or ArAr + ) and Ar + (or Ar + Ar)π stacking. In addition, Ar + -L-Ar-L-NR3 + SDA-like NR3 + It may or may not interact with Ar. + Whether it interacts significantly with Ar or not, NR3 + Some provide extra volume for this type of SDA.

[0049] Examples of uncharged aromatic rings include, but are not limited to, phenyl, substituted phenyl, naphthyl, substituted naphthyl, and the like. The aforementioned substituted uncharged aromatic rings include those wherein one or more C of the uncharged aromatic ring is independently substituted with a C1-C6 alkyl (branched or linear) or a C5-C6 cycloalkyl. In addition, uncharged N-containing aromatic rings may be used, but the nitrogen should be protected during one or more steps of the synthesis so that it is not alkylated and is in a cationic form in the final SDA.

[0050] Examples of N-containing cationic aromatic rings include, but are not limited to, pyridine Substituted pyridine Imidazole Substituted Imidazole Pyrazole Substituted pyrazoles Pyrazine Substituted pyrazines Pyrimidine Substituted pyrimidine The aforementioned substituted N-containing cationic aromatic ring includes one in which one or more C of the N-containing cationic aromatic ring is independently substituted with a C1-C6 alkyl group (branched or linear) or a C5-C6 cycloalkyl group.

[0051] The N-containing cationic aromatic part of SDA can be catalyzed by OH - 、F - , Cl - Br - or I - balance.

[0052] Examples of fused aromatic ring structures having both a N-containing cationic portion and an uncharged portion include, but are not limited to, benzimidazole Substituted benzimidazoles Among them, benzimidazole One or more C of the aromatic ring structure may be independently substituted with a C1-C6 alkyl group (branched or linear) or a C5-C6 cycloalkyl group. -、F - , Cl - Br - or I - balance.

[0053] Examples of linking groups include, but are not limited to, methylene chains of 3-6 carbon atoms in length.

[0054] Compound EW is a non-limiting example of an SDA described herein.

[0055]

[0056] Where R1-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0057]

[0058] Where R1-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0059]

[0060] Where R1-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0061]

[0062] Where R1-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0063]

[0064] Where R1-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0065]

[0066] Where R1-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0067]

[0068] Where R2-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R2-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0069]

[0070] Where R2-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R2-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0071]

[0072] Where R2-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R2-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 Each is H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0073]

[0074] wherein R1-R4 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R4 are each H, and R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0075]

[0076] wherein R1-R4 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R4 are each H, and R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0077]

[0078] wherein R1-R4 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R4 are each H, and R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0079]

[0080] wherein R2-R9 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R2-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R9 are each H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0081]

[0082] wherein R2-R9 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R2-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R9 are each H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0083]

[0084] wherein R2-R9 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R2-R5 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R9 are each H); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0085]

[0086] wherein R1-R4 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R6-R 13 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl (preferably, R1-R4 are each H; R6-R 10 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl, and R 11 -R 13 each is CH3); and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0087]

[0088] wherein R2-R3 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl; and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0089]

[0090] wherein R2-R3 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl; and wherein N + OH - 、F - , Cl - Br - or I - balance;

[0091]

[0092] wherein R2-R3 are independently H, C1-C6 alkyl (branched or linear) or C5-C6 cycloalkyl; and wherein N + OH - 、F - , Cl - Br - or I - balance.

[0093] Advantageously, the SDA described herein has a simple synthesis with very few steps (in some cases, one step). Typically, a pyridine, imidazole, pyrazole or pyrazine precursor is reacted with a 1-halo-(3-6)-phenylalkane or a derivative thereof (wherein the halogen is preferably bromine, 3-6 represents a C3-C6 linker, and the phenyl group may be derivatized). Furthermore, the reaction conditions are mild and no additional expensive or hazardous chemicals are required.

[0094] Synthesis of molecular sieves

[0095] The present disclosure also provides a method for preparing a molecular sieve, the method comprising the following steps: i) preparing a synthesis mixture capable of forming a molecular sieve, the synthesis mixture comprising one or more tetrahedral element sources, optionally, a hydroxide ion source, optionally, a halide ion source, and optionally, an alkali metal / alkaline earth metal ion source, the synthesis mixture further comprising an SDA capable of intramolecular π-stacking as described herein; ii) heating the synthesis mixture under crystallization conditions for a sufficient time (e.g., from about 2 hours to about 100 days) to form crystals of the molecular sieve, and iii) recovering the crystals of the molecular sieve from the synthesis mixture. "Tetrahedral element" as used herein refers to an element capable of forming a tetrahedral conformation in a molecular sieve, and does not imply any conformational or valence constraints of the element source.

[0096] Tetrahedral elements include, but are not limited to, Li, Be, Al, B, P, Si, Ga, Ge, Zn, Cr, Mg, Fe, Co, Ni, Mn, As, In, Sn, Sb, Ti, Zr, and any combination thereof. Preferably, the tetrahedral element comprises one or more elements selected from Si, Al, B, P, Ge, Sn, Ti, and Zr. More preferably, the tetrahedral atom is Si, Ge, and any combination thereof.

[0097] Suitable sources of tetrahedral element Y depend on the element Y selected. Examples of silicon sources include, but are not limited to, colloidal suspensions of silica, precipitated silica alkali metal silicates, tetraalkyl orthosilicates, aluminosilicate pozzolans (e.g., metakaolin and fly ash), other siliceous zeolites, and any combination thereof. Examples of germanium sources include, but are not limited to, germanium oxide, germanium alkoxides, germanium-containing zeolites, and any combination thereof. Examples of aluminum sources include, but are not limited to, aluminum nitrate, aluminum sulfate, aluminum hydroxide, sodium aluminate, aluminum oxide, alumina sol, aluminosilicate pozzolans, alumina trihydrate, aluminum alkoxides (e.g., aluminum isopropoxide), aluminum metal, and any combination thereof. Examples of boron sources include, but are not limited to, boric acid, water-soluble borates, and any combination thereof. Examples of phosphorus sources include, but are not limited to, phosphoric acid, organic phosphates (e.g., triethyl phosphate and tetraethylammonium phosphate), aluminum phosphates, and any combination thereof.

[0098] Optionally, the synthesis mixture also contains a halide ion source, which can be selected from chloride, bromide or fluoride. The halide ion source can be any compound that can release halide ions in the molecular sieve synthesis mixture. If the quaternary ammonium is used in its unexchanged form, halide ions can also be derived from quaternary ammonium. Examples of halide ion sources include, but are not limited to, salts containing one or more metal halide ions (for example, wherein the metal is sodium, potassium, calcium, magnesium, strontium or barium), ammonium fluoride or tetraalkylammonium fluoride. If the halide ion is fluoride, suitable halide ion sources are HF or ammonium fluoride.

[0099] Optionally, the synthesis mixture also contains an alkali metal / alkaline earth metal source. If present, the alkali metal / alkaline earth metal is preferably selected from sodium, potassium and a mixture of sodium and potassium. The sodium source can be sodium hydroxide or sodium aluminate.

[0100] The molecular sieves described herein may include, but are not limited to, silica molecular sieves, aluminosilicate molecular sieves, borosilicate molecular sieves, aluminoborosilicate molecular sieves or germanosilicate molecular sieves, aluminophosphate molecular sieves, silicoaluminophosphate molecular sieves or metalloaluminophosphate molecular sieves.

[0101] The synthesis of the molecular sieves described herein generally comprises reacting a source of a specified molecular sieve composition in the presence of SDA and water to form a specified molecular sieve composition. The reaction is generally continued at an elevated temperature (e.g., from about 75° C. to about 200° C.) for a suitable length of time (e.g., from about 2 hours to about 20 days) to allow the formation of molecular sieve crystals.

[0102] The molar ratio of tetrahedral elements to SDA in the reaction mixture may be from about 0.1 to about 30, from about 0.5 to about 15, or from about 1 to about 10, or from about 1 to about 5.

[0103] When two or more tetrahedral elements are present, the relative concentrations of the various components in the reaction mixture (based on the molar ratio of atomic component to atomic component, such as the molar ratio of atomic Si to atomic Al or the molar ratio of atomic Al to atomic B) can be any suitable value based on the desired amount of each in the final molecular sieve. Without wishing to be limiting, the molar ratio of the first atomic component (present at a concentration equal to or higher than the second atomic component) to the second atomic component in the reaction mixture can be from about 1 to about 1000, or from about 1 to about 100, or from about 1 to about 5, or from about 4 to about 30, or from about 4 to about 20, or from about 30 to about 60, or from about 50 to 100, or from about 75 to 200, or from about 100 to about 1000.

[0104] The molar ratio of water to tetrahedral element (or total tetrahedral elements when more than one tetrahedral element is used) in the reaction mixture can be from about 2 to about 80, or from about 5 to about 30, or from about 10 to about 30, or from about 25 to about 50, or from about 30 to about 60.

[0105] In some cases, the reaction mixture can be seeded with a small amount of molecular sieves. The molecular sieve continues to grow from the seed under reaction conditions. Therefore, the seed is usually, but not necessarily has a desired morphology (topographical) framework (for example, RHO framework, LTA framework, ITE framework, RTH framework, ITE / RTH symbiotic framework, IWV framework, IFW framework, *CTH framework, SAS framework, POS framework or MWW framework) and composition (for example, silica molecular sieve, aluminosilicate molecular sieve, borosilicate molecular sieve, aluminoborosilicate molecular sieve, germanosilicate molecular sieve, aluminophosphate molecular sieve or silicoaluminophosphate molecular sieve). The amount of seed in the reaction mixture can be about 0.01ppm to about 10,000ppm by weight of the reaction mixture, or about 100ppm to about 5,000ppm.

[0106] The molecular sieve synthesis may be conducted at a temperature of at least about 75°C, or from about 75°C to about 200°C, or from about 100°C to about 185°C, or from about 135°C to about 175°C.

[0107] The molecular sieve synthesis may be carried out for a period of at least about 2 hours, or from about 34 hours to about 20 days, or from about 72 hours to about 15 days, or from about 4 days to about 10 days.

[0108] Generally, the time and temperature of the reaction are interrelated. Generally, lower temperatures require longer reaction times. In addition, if seed crystals are included, the reaction time can be reduced even at lower reaction temperatures.

[0109] The methods described herein may further include calcining the molecular sieve at a temperature of about 500°C to about 900°C, or 550°C to about 850°C, or 600°C to about 800°C.

[0110] Depending on SDA, reaction conditions and reactants, the molecular sieve formed by the method described herein can have a variety of frameworks with large cages, large cavities and / or large or ultra-large pores. Examples of frameworks include, but are not limited to, RHO frameworks, LTA frameworks, ITE frameworks, RTH frameworks, ITE / RTH symbiotic frameworks, IWV frameworks, IFW frameworks, *CTH frameworks, SAS frameworks, POS frameworks and MWW frameworks. In some cases, particles with a first framework and other particles with a second framework can be produced in the same reaction mixture. Each framework is discussed in more detail herein.

[0111] Advantageously, these frameworks with large cages, large cavities and / or large or extra large pores are obtained with SDA in a direct synthesis without the use of expensive reactants and intermediates. In addition, as shown in the examples, the SDA described herein can be used to synthesize molecular sieves with previously unrealized combinations of compositions and frameworks. For example, RHO frameworks composed of borosilicates or aluminoborosilicates with high silicon content can be achieved.

[0112] After producing molecular sieve, optionally, at least a portion of boron, aluminum and / or germanium (when present) can be released or removed from the structure. In some cases, this can be achieved by treating the molecular sieve with acid and / or boiling in hot water. Although high siliceous molecular sieve can be directly synthesized, this method can be used to increase the silicon dioxide content of any of the molecular sieves. In some cases, when the framework has a large cage and / or large cavity but has a small to medium hole, compared with a macroporous framework, the amount of aluminum released or removed from the molecular sieve can be reduced.

[0113] Thus, even higher silica concentrations can be achieved, such as a ratio of atomic Si to atomic B (or Al or Ge) greater than or equal to 11. Because almost all of the B (or Al or Ge) can be removed, the molar ratio of atomic Si to atomic B (or Al or Ge) can be infinitely high. The molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) can contain B (or Al or Ge) at less than 5% by weight of the molecular sieve, or less than 1% by weight of the molecular sieve, or less than 0.1% by weight of the molecular sieve, or less than 0.01% by weight of the molecular sieve.

[0114] Examples of acids suitable for treating the molecular sieve include, but are not limited to, sulfuric acid, hydrochloric acid, acetic acid, nitric acid, and any combination thereof.

[0115] RHO skeleton

[0116] The RHO framework is composed of Linde A-type (LTA) cages connected to adjacent LTA cages via 8-rings to create double 8-rings.

[0117] If synthesized, it is difficult to synthesize high-siliceous RHO-type molecular sieves (e.g., high-siliceous aluminosilicate molecular sieves, high-siliceous borosilicate molecular sieves, and high-siliceous aluminoborosilicate molecular sieves) using known SDA in the art. For example, high-siliceous aluminosilicate molecular sieves in the art typically have an atomic Si to atomic Al ratio of 3-6. In another example, borosilicate RHO-type molecular sieves do not appear to have been synthesized before. As illustrated in the examples, the SDA of the present disclosure may have such a ratio of 8 or greater and even 11 or greater.

[0118] The Rho molecular sieve described herein can be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve or an aluminoborosilicate molecular sieve. In addition, the Rho molecular sieve described herein can have other compositions corresponding to tetrahedral elements and / or alkali metal / alkaline earth metal sources that are not in the aforementioned composition.

[0119] The Rho borosilicate molecular sieve or the Rho aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 1 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 8 to about 25, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Rho aluminosilicate molecular sieve or the Rho aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 1 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0120] The Rho molecular sieves of the present disclosure that have been treated to release or remove B may contain B at less than 5 weight percent of the molecular sieve, or less than 1 weight percent of the molecular sieve, or less than 0.1 weight percent of the molecular sieve, or less than 0.01 weight percent of the molecular sieve.

[0121] As-synthesized and treated (e.g., calcined or acid-treated) borosilicate Rho molecular sieves can have characteristic X-ray diffraction (XRD) patterns, the primary (most intense) reflection lines of which can be shown in Table 1 (as-synthesized form) and Table 2 (calcined form). As a function of the specific composition and SDA used in the synthesis, variations can occur. Thus, relative peak areas and d-spacings (" ") are expressed as ranges in Tables 1 and 2.

[0122] Table 1

[0123]

[0124] Table 2

[0125]

[0126]

[0127] As-synthesized and treated (e.g., calcined or acid-treated) aluminosilicate Rho molecular sieves may have characteristic X-ray diffraction (XRD) patterns, the primary (most intense) reflection lines of which may be shown in Table 3 (in the as-synthesized form) and Table 4 (in the calcined form). As a function of the specific composition and SDA used in the synthesis, may vary. Thus, the relative peak height intensity and Expressed as ranges in Tables 3 and 4.

[0128] Table 3

[0129]

[0130] Table 4

[0131]

[0132]

[0133] LTA skeleton

[0134] The LTA framework is described in Atlas of Zeolite Framework Types, 6th edition.

[0135] Generally, aluminophosphates and silicoaluminophosphate molecular sieves (especially pure aluminophosphates) having an LTA framework are difficult to synthesize. In addition, the LTA framework in a highly siliceous form, in which the molar ratio of atomic Si to atomic Al is greater than 5, is also difficult to prepare. However, the SDA described herein easily forms the composition having an LTA framework. In addition, the introduction of elements other than aluminum, silicon and phosphate into the structure demonstrated in the examples is unexpected.

[0136] The Lta molecular sieve described herein can be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve, a germanosilicate molecular sieve, an aluminophosphate molecular sieve or a silicoaluminophosphate molecular sieve. In addition, the Lta molecular sieve described herein can have other compositions corresponding to tetrahedral elements and / or alkali metal / alkaline earth metal sources that are not in the aforementioned composition. For example, the magnesium source and / or nickel source contained in the reaction mixture can cause magnesium and / or nickel to be introduced into the LTA framework instead of aluminum.

[0137] The Lta borosilicate molecular sieve or the Lta aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 1 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Lta aluminosilicate molecular sieve or the Lta aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 1 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. Lta silicoaluminophosphate molecular sieves may have a molar ratio of atomic Si to atomic Al of about 0.05 to about 0.4, or about 0.05 to about 0.1, or about 0.1 to about 0.2, or about 0.2 to about 0.3, or about 0.3 to about 0.4. Lta germanosilicate molecular sieves may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0138] The LTA-type molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 weight % of the molecular sieve, or less than 1 weight % of the molecular sieve, or less than 0.1 weight % of the molecular sieve, or less than 0.01 weight % of the molecular sieve.

[0139] ITE frame

[0140] Typically, ITE frameworks (particularly ITE frameworks having an aluminosilicate composition) are produced using SDA, which is expensive and / or difficult to prepare.

[0141] The Ite molecular sieve described herein may be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve.

[0142] The Ite borosilicate molecular sieve or the Ite aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 3 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 3 to about 25, or about 3 to about 5, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Ite aluminosilicate molecular sieve or the Ite aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 3 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 3 to about 25, or about 3 to about 5, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Ite germanosilicate molecular sieve can have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when acid and / or hot water is used to release or remove Ge as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0143] The Ite molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 wt % of the molecular sieve, or less than 1 wt % of the molecular sieve, or less than 0.1 wt % of the molecular sieve, or less than 0.01 wt % of the molecular sieve.

[0144] As-synthesized and treated (e.g., calcined or acid-treated) Ite molecular sieves can have characteristic X-ray diffraction (XRD) patterns. The basic (strongest) reflection lines of aluminosilicate Ite molecular sieves are listed in Table 4 (in the form of as-synthesized). As a function of the specific composition and SDA used in the synthesis, they can vary. Therefore, the relative peak height intensity and Expressed as ranges in Table 4.

[0145] Table 4

[0146]

[0147] RTH skeleton

[0148] Typically, RTH frameworks (particularly RTH frameworks having an aluminosilicate composition) are produced using SDA, which is expensive and / or difficult to prepare.

[0149] The Rth molecular sieve described herein may be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve.

[0150] The Rth borosilicate molecular sieve or Rth aluminoborosilicate molecular sieve can have a molar ratio of atomic Si to atomic B of about 3 or greater (including infinitely high when acid and / or hot water is used to release or remove B as described above), or about 3 to about 100, or about 3 to about 50, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100. The Rth aluminosilicate molecular sieve or Rth aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 3 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 3 to about 100, or about 3 to about 50, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 2, or about 20 to about 50, or about 20 to about 100. The Rth germanosilicate molecular sieve may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 100, or about 1 to about 50, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100.

[0151] The Rth molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 weight % of the molecular sieve, or less than 1 weight % of the molecular sieve, or less than 0.1 weight % of the molecular sieve, or less than 0.01 weight % of the molecular sieve.

[0152] Rth molecular sieves as synthesized and treated (e.g., calcined or acid-treated) can have characteristic X-ray diffraction (XRD) patterns. The basic (strongest) reflection lines of aluminosilicate Rth molecular sieves are listed in Table 5 (in the form as synthesized). As a function of the specific composition and SDA used in the synthesis, they can vary. Therefore, the relative peak height intensity and Expressed as ranges in Table 5.

[0153] Table 5

[0154]

[0155] ITE / RTH symbiotic framework

[0156] ITE / RTH symbiotic frameworks are individual particles that have both ITE and RTH frameworks. Because the crystal structure symmetry of these two frameworks is very similar, the ITE framework layer can grow next to the RTH framework layer in the same crystal, also known as epitaxial symbiosis.

[0157] The Ite / Rth molecular sieve described herein may be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve.

[0158] The Ite / Rth borosilicate molecular sieve or the Ite / Rth aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 15 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 15 to about 100, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100. The Ite / Rth aluminosilicate molecular sieve or the Ite / Rth aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 15 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 15 to about 100, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100. Ite / Rth germanosilicate molecular sieves can have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when acid and / or hot water is used to release or remove Ge as described above), or about 1 to about 100, or about 1 to about 50, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100.

[0159] The Ite / Rth molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 weight % of the molecular sieve, or less than 1 weight % of the molecular sieve, or less than 0.1 weight % of the molecular sieve, or less than 0.01 weight % of the molecular sieve.

[0160] IWV skeleton

[0161] The Iwv molecular sieve described herein can be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve. In addition, the Iwv molecular sieve described herein can have other compositions corresponding to tetrahedral elements and / or alkali metal / alkaline earth metal sources that are not in the aforementioned composition.

[0162] The Iwv borosilicate molecular sieve or Iwv aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 3 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 3 to about 25, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Iwv aluminosilicate molecular sieve or Iwv aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 1 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. Iwv silicoaluminophosphate molecular sieves may have a molar ratio of atomic Si to atomic Al of about 0.05 to about 0.4, or about 0.05 to about 0.1, or about 0.1 to about 0.2, or about 0.2 to about 0.3, or about 0.3 to about 0.4. Iwv germanosilicate molecular sieves may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0163] The Iwv molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 weight % of the molecular sieve, or less than 1 weight % of the molecular sieve, or less than 0.1 weight % of the molecular sieve, or less than 0.01 weight % of the molecular sieve.

[0164] The Iwv molecular sieves as synthesized and treated (e.g., calcined or acid-treated) may have characteristic X-ray diffraction (XRD) patterns. The basic (strongest) reflection lines of the aluminosilicate Iwv molecular sieves, silicate Iwv molecular sieves, and germanosilicate Iwv molecular sieves are shown in Tables 6, 7, and 8, respectively (all in the form of the as-synthesized form). As a function of the specific composition and SDA used in the synthesis, changes may occur. Therefore, the relative peak height intensity and Expressed as ranges in Tables 6, 7 and 8.

[0165] Table 6

[0166]

[0167] Table 7

[0168]

[0169] Table 8

[0170]

[0171] IFW Skeleton

[0172] IFW frameworks having all-silica or aluminosilicate compositions have not been directly synthesized previously. In addition, other compositions having IFW frameworks are usually produced using SDA, which is expensive and / or difficult to prepare.

[0173] The Ifw molecular sieve described herein may be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve.

[0174] The Ifw borosilicate molecular sieve or Ifw aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 3 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 3 to about 100, or about 3 to about 50, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100. The Ifw aluminosilicate molecular sieve or Ifw aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 15 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 15 to about 100, or about 15 to about 50, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100. Ifw silicoaluminophosphate molecular sieves may have a molar ratio of atomic Si to atomic Al of about 0.05 to about 0.4, or about 0.05 to about 0.1, or about 0.1 to about 0.2, or about 0.2 to about 0.3, or about 0.3 to about 0.4. Ifw germanosilicate molecular sieves may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 100, or about 1 to about 50, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25, or about 20 to about 50, or about 20 to about 100.

[0175] The Ifw molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 wt % of the molecular sieve, or less than 1 wt % of the molecular sieve, or less than 0.1 wt % of the molecular sieve, or less than 0.01 wt % of the molecular sieve.

[0176] As-synthesized and treated (e.g., calcined or acid-treated) Ifw molecular sieves can have characteristic X-ray diffraction (XRD) patterns. The fundamental (strongest) reflection lines of the aluminoborosilicate Ifw molecular sieves are listed in Table 9 (in the form as-synthesized). As a function of the specific composition and SDA used in the synthesis, they can vary. Therefore, the relative peak height intensity and Expressed as ranges in Table 9.

[0177] Table 9

[0178]

[0179] *CTH skeleton

[0180] Typically, molecular sieves having a *CTH framework previously required the presence of germanium in the reaction mixture. However, as shown in the Examples herein, all-silica and borosilicate *Cth molecular sieves can be synthesized using the SDA described herein.

[0181] The *Cth molecular sieve described herein may be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve. The *Cth molecular sieve may not contain Ge (or may not contain Ge).

[0182] The *Cth borosilicate molecular sieve or the *Cth aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 4 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 4 to about 40, or about 4 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25, or about 20 to about 40. The *Cth aluminosilicate molecular sieve or the *Cth aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 4 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 4 to about 25, or 1 to about 5, or about 4 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. *Cth silicoaluminophosphate molecular sieves may have a molar ratio of atomic Si to atomic Al of about 0.05 to about 0.4, or about 0.05 to about 0.1, or about 0.1 to about 0.2, or about 0.2 to about 0.3, or about 0.3 to about 0.4. *Cth germanosilicate molecular sieves may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0183] The *Cth molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 weight % of the molecular sieve, or less than 1 weight % of the molecular sieve, or less than 0.1 weight % of the molecular sieve, or less than 0.01 weight % of the molecular sieve.

[0184] The *Cth molecular sieves as synthesized and treated (e.g., calcined or acid-treated) can have characteristic X-ray diffraction (XRD) patterns. The fundamental (strongest) reflection lines of the all-silica *Cth molecular sieves are listed in Table 10 (in the form as synthesized). As a function of the specific composition and SDA used in the synthesis, they can vary. Therefore, the relative peak height intensity and Expressed as ranges in Table 10.

[0185] Table 10

[0186]

[0187]

[0188] SAS skeleton

[0189] SAS frameworks having metalloaluminophosphate compositions have been prepared previously, but not SAS frameworks having silicoaluminophosphate compositions.

[0190] The SAS molecular sieve described herein can be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve, a germanosilicate molecular sieve, an aluminophosphate molecular sieve, a silicoaluminophosphate molecular sieve, and a metal aluminophosphate molecular sieve.

[0191] The Sas borosilicate molecular sieve or the Sas aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 1 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or from about 1 to about 25, or from about 1 to about 5, or from about 1 to about 8, or from about 5 to about 12, or from about 9 to about 16, or from about 10 to about 13, or from about 11 to about 25, or from about 15 to about 25. The Sas aluminosilicate molecular sieve or the Sas aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 1 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or from about 1 to about 25, or from about 1 to about 5, or from about 1 to about 8, or from about 5 to about 12, or from about 9 to about 16, or from about 10 to about 13, or from about 11 to about 25, or from about 15 to about 25. The Sas silicoaluminophosphate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 0.05 to about 0.4, or about 0.05 to about 0.1, or about 0.1 to about 0.2, or about 0.2 to about 0.3, or about 0.3 to about 0.4. The Sas germanosilicate molecular sieve may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0192] The Sas molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 wt % of the molecular sieve, or less than 1 wt % of the molecular sieve, or less than 0.1 wt % of the molecular sieve, or less than 0.01 wt % of the molecular sieve.

[0193] POS skeleton

[0194] Although POS frameworks have been previously prepared in germanosilicate compositions, the synthesis described herein uses SDA with the advantages described herein.

[0195] The Pos molecular sieve described herein can be a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve, a germanosilicate molecular sieve, an aluminophosphate molecular sieve, and a silicoaluminophosphate molecular sieve.

[0196] The Pos borosilicate molecular sieve or the Pos aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic B of about 1 or greater (including infinitely high when B is released or removed using acid and / or hot water as described above), or about 3 to about 25, or about 3 to about 5, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Pos aluminosilicate molecular sieve or the Pos aluminoborosilicate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 3 or greater (including infinitely high when Al is released or removed using acid and / or hot water as described above), or about 3 to about 25, or about 3 to about 5, or about 3 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25. The Pos silicoaluminophosphate molecular sieve may have a molar ratio of atomic Si to atomic Al of about 0.05 to about 0.4, or about 0.05 to about 0.1, or about 0.1 to about 0.2, or about 0.2 to about 0.3, or about 0.3 to about 0.4. The Pos germanosilicate molecular sieve may have a molar ratio of atomic Si to atomic Ge of about 1 or greater (including infinitely high when Ge is released or removed using acid and / or hot water as described above), or about 1 to about 25, or about 1 to about 5, or about 1 to about 8, or about 5 to about 12, or about 9 to about 16, or about 10 to about 13, or about 11 to about 25, or about 15 to about 25.

[0197] The Pos molecular sieve of the present disclosure that has been treated to release or remove B (or Al or Ge) may contain B (or Al or Ge) at less than 5 wt % of the molecular sieve, or less than 1 wt % of the molecular sieve, or less than 0.1 wt % of the molecular sieve, or less than 0.01 wt % of the molecular sieve.

[0198] MWW Skeleton

[0199] The Mww molecular sieves described herein can be silica molecular sieves, aluminosilicate molecular sieves, borosilicate molecular sieves, and aluminoborosilicate molecular sieves. Previously produced MWW frameworks use SDA, which is expensive and / or difficult to prepare.

[0200] The Mww borosilicate molecular sieve or Mww aluminoborosilicate molecular sieve can have a molar ratio of atomic Si to atomic B of about 3 or greater (including infinitely high when acid and / or hot water is used to release or remove B as described above), or from about 3 to about 750, or from about 3 to about 5, or from about 3 to about 8, or from about 5 to about 12, or from about 9 to about 16, or from about 10 to about 13, or from about 11 to about 25, or from about 15 to about 25, or from about 20 to 100, or from about 50 to about 250, or from about 200 to 500, or from about 250 to about 700. The Mww aluminosilicate molecular sieve or Mww aluminoborosilicate molecular sieve can have a molar ratio of atomic Si to atomic Al of about 3 or greater (including infinitely high when acid and / or hot water is used to release or remove Al as described above), or from about 3 to about 750, or from about 3 to about 5, or from about 3 to about 8, or from about 5 to about 12, or from about 9 to about 16, or from about 10 to about 13, or from about 11 to about 25, or from about 15 to about 25, or from about 20 to 100, or from about 50 to about 250, or from about 200 to 500, or from about 250 to about 700.

[0201] The Mww molecular sieves of the present disclosure that have been treated to release or remove B (or Al) may contain B (or Al) at less than 5 wt % of the molecular sieve, or less than 1 wt % of the molecular sieve, or less than 0.1 wt % of the molecular sieve, or less than 0.01 wt % of the molecular sieve.

[0202] application

[0203] The molecular sieve of the present invention (in the original state of post-synthesis treatment or production) can be used as an adsorbent, for example, in a mixture comprising carbon dioxide and one or more alkanes (e.g., methane, ethane, propane and / or butane) and / or a mixture comprising carbon dioxide and oxygen, nitrogen, H2S, SOx and / or NOx to separate carbon dioxide. The separation method can adopt the equilibrium selectivity of the molecular sieve for carbon dioxide relative to the other components (one or more) of the mixture, the kinetic selectivity of the molecular sieve, or both the equilibrium selectivity and kinetic selectivity of the molecular sieve. As a non-limiting example, a RHO type molecular sieve with a molar ratio of atomic Si to atomic B of about 8 to about 30 can generally have an adsorption capacity of about 0.8mmol / g to about 2.0mmol / g at about 1atm (about 100kPa) for CO2. Alternatively or in addition, the molecular sieve can be used as a catalyst to promote one or more organic compound conversion processes, including many organic compound conversion processes of current commercial / industrial importance.

[0204] The molecular sieves of the present invention (either treated after synthesis or as produced) can be used as supports in catalyst systems. Such catalysts can be used, for example, to reduce NO in gas streams (e.g., exhaust gas streams from combustion operations). x In order to reduce NOx , copper is the preferred transition metal that the molecular sieve can be impregnated or exchanged to produce the catalyst. Other possible metals include zinc, vanadium, chromium, manganese, iron, cobalt, nickel, rhodium, palladium, platinum and molybdenum. In addition to transition metals, alkali metals or alkaline earth metals may also be present in the catalyst to promote NO x Reduction. These metals include alkaline earth metals, sodium, potassium, rubidium, cesium, magnesium, calcium and barium. In addition, a steam-stabilized amount of titanium, zirconium or rare earth may be included. The metal may be impregnated into the molecular sieve as a metal or ion. The metal may be about 1 wt % to about 10 wt %, or about 2 wt % to about 5 wt % of the catalyst system (e.g., impregnated molecular sieve).

[0205] In an exemplary embodiment of preparing the catalyst, a steam-stabilized amount of titanium or zirconium cations or a mixture of these metal compounds is included in the additive by treating the molecular sieve (either as treated after synthesis or as produced) with any titanium or zirconium compound (e.g., aqueous solutions of titanium tetramethoxide and zirconium acetate) that can be closely associated with the molecular sieve. The introduction of titanium or zirconium can be carried out after ion exchange of copper ions. Alternatively, impregnation with copper ions can also be carried out simultaneously with an aqueous solution containing, for example, divalent copper cations and soluble titanium or soluble zirconium compounds. Additional synthesis and catalyst system preparation details can be found in U.S. Patent No. 6,143,261, which is incorporated herein by reference.

[0206] In yet another example, the molecular sieves described herein may also be used as catalysts in reactions such as alkylation, transalkylation, dealkylation, hydrodecylation, disproportionation, oligomerization, and dehydrocyclization, especially molecular sieves having large or medium pores.

[0207] In another example, molecular sieves can be used as catalysts in the synthesis of methylamines (e.g., monomethylamine, dimethylamine, and trimethylamine) from methanol (and / or dimethyl ether) and ammonia. The concentration of the reactants (methanol (and / or dimethyl ether) and ammonia) can provide a carbon to nitrogen molar ratio of about 0.2 to about 1.5, or about 0.7 to about 1.3. The reaction temperature is about 250°C to about 450°C, or about 300°C to about 425°C. Additional synthesis details can be found in U.S. Patent No. 5,569,785, which is incorporated herein by reference.

[0208] In the case of many catalysts used in organic compound (hydrocarbon) conversion processes, it may be desirable to combine molecular sieves with another material that tolerates the temperature and other conditions used in organic conversion processes. Such materials can include active and inactive materials and synthetic or naturally occurring molecular sieves, and inorganic materials, such as clay, silicon dioxide and / or metal oxides, such as aluminum oxide. The latter can be naturally occurring or in the form of a gelatinous precipitate or gel comprising a mixture of silicon dioxide and metal oxides. The material used in combination with molecular sieves (i.e., combined with it and / or present during the synthesis of active new crystals) can tend to change the conversion rate and / or selectivity of the catalyst in certain organic conversion processes. Inactive materials can be appropriately used as diluents to control the conversion amount in a given method, so that products can be obtained in an economical and orderly manner without using other (more expensive) means to control the reaction rate. These materials can be incorporated into naturally occurring clays (such as bentonite and kaolin) to improve the compressive strength of the catalyst under commercial operating conditions. The material (i.e., clay, oxide, etc.) can be used as a binder for the catalyst. Providing a catalyst with good compressive strength may be desirable because in commercial use it may be desirable to prevent the catalyst from breaking down into powdery material (abrasion). These clay and / or oxide binders are generally employed solely for the purpose of improving the compressive strength of the catalyst.

[0209] Naturally occurring clays that can be composited with molecular sieves can include, but are not limited to, montmorillonite and kaolin families, which include sub-bentonites, and kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or other clays whose main mineral components are halloysite, kaolinite, dickite, nacrite or anthracite. Such clays can be used in their original state as originally mined or initially calcined, acid treated or chemically modified. Binders that can be used for composites with molecular sieves can additionally or alternatively include inorganic oxides, such as silicon dioxide, zirconium oxide, titanium oxide, magnesium oxide, beryllium oxide, aluminum oxide and mixtures thereof.

[0210] As an alternative or supplement to the aforementioned materials, the molecular sieve can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania and / or one or more ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

[0211] The relative proportions of the molecular sieve and the inorganic oxide matrix can vary over a wide range, with the molecular sieve content ranging from about 1 wt % to about 90 wt %, and more typically, particularly when the composite is prepared in bead form, ranging from about 2 wt % to about 80 wt % of the composite. Exemplary matrix content ranges may include about 10 wt % to about 50 wt %.

[0212] Numerical ranges used herein include the values ​​recited in the range. For example, a numerical range of "1 wt % to 10 wt %" includes 1 wt % and 10 wt % within the range.

[0213] Example Implementation

[0214] A first non-limiting example embodiment of the present disclosure is a method comprising: subjecting a source selected from a tetrahedral element source to a reaction mixture selected from Ar + -L-Ar, Ar + -L-Ar-L-Ar + and Ar + -L-Ar-L-NR3 + to produce a molecular sieve in the presence of a structure directing agent (SDA) wherein Ar + refers to a cationic aromatic ring containing N, Ar refers to an uncharged aromatic ring, L is a methylene chain of 3-6 carbon atoms, NR3 + Refers to quaternary ammonium. The first non-limiting example embodiment may include one or more of the following elements: Element 1: wherein the N-containing cationic aromatic ring is selected from: pyridine Substituted pyridine Imidazole Substituted Imidazole Pyrazole Substituted pyrazoles Pyrazine Substituted pyrazines Pyrimidine and substituted pyrimidines Element 2: wherein the uncharged aromatic ring is selected from the group consisting of phenyl, substituted phenyl, naphthyl, and substituted naphthyl; Element 3: wherein the SDA is selected from the group consisting of Compound E, Compound F, Compound G, Compound H, Compound I, Compound J, Compound K, Compound L, Compound M, Compound N, Compound O, Compound P, Compound Q, Compound R, Compound S, Compound T, and any combination thereof; Element 4: wherein the tetrahedral element comprises Si, and wherein the aqueous reaction mixture has a molar ratio of atomic Si to structure directing agent of from about 1 to about 20; Element 5: wherein the tetrahedral element comprises Si, and wherein the aqueous reaction mixture has a molar ratio of water to atomic Si of from about 2 to about 80; Element 6: wherein the tetrahedral element is selected from the group consisting of Li, Be, Al, B, P, Si, Ga, Ge, Zn, Cr, Mg, Fe, Co, Ni, Mn, As, In, Sn, Sb, Ti, Zr, and any combination thereof; Element 7: wherein the reaction mixture further comprises a source of hydroxide ions; Element 8: wherein the reaction mixture further comprises a halide ion source; Element 9: wherein the reaction mixture also comprises an alkali metal / alkaline earth metal ion source; Element 10: wherein the reaction mixture further comprises molecular sieve seeds; Element 11: wherein the reaction is carried out at a temperature of about 75°C to about 200°C; Element 12: wherein the reaction lasts for a period of about 2 hours to about 28 days; Element 13: wherein the molecular sieve has a composition selected from the group consisting of silica, aluminosilicates, borosilicates, aluminoborosilicates, germanosilicates, aluminophosphates, silicoaluminophosphates and metalloaluminophosphates; Element 14: wherein the molecular sieve has a framework selected from the group consisting of RHO framework, LTA framework, ITE framework, RTH framework, ITE / RTH intergrowth framework, ITE / RTH intergrowth framework, IWV framework, IFW framework, *CTH framework, SAS framework, POS framework and MWW framework; Element 15: the method further comprises: calcining the molecular sieve at about 500°C to about 900°C; Element 16: the method further comprises: exposing the molecular sieve to an acid; and Element 17: the method further comprises: exposing the molecular sieve to boiling water. Examples of combinations include, but are not limited to, element 1 and element 2 combined; element 1 and / or element 2 combined with one or more of elements 4-9, and optionally further combined with elements 10-12; element 3 combined with one or more of elements 4-9, and optionally further combined with elements 10-12; elements 13 and 14 combined; element 13 and / or element 14 combined with one or more of elements 15-17; element 1 and / or element 2 combined with element 13 and / or element 14; and element 3 combined with element 13 and / or element 14.

[0215] A second non-limiting example embodiment of the present disclosure is a method comprising: causing a source selected from a tetrahedral element source to react in the presence of ArAr + -L-Ar+ Ar is reacted in the presence of a structure directing agent (SDA) to produce a molecular sieve, wherein L is a methylene chain of 3 to 6 carbon atoms, and ArAr + and Ar + Ar is a fused aromatic ring structure comprising both a N-containing cationic moiety and an uncharged moiety. A second non-limiting example embodiment may include one or more of the following elements: Element 18: wherein the SDA is selected from the group consisting of Compound U, Compound V, Compound W, and any combination thereof; Element 19: wherein the tetrahedral element comprises Si; and wherein the aqueous reaction mixture has a molar ratio of atomic Si to structure directing agent of about 1 to about 15; Element 20: wherein the tetrahedral element comprises Si; and wherein the aqueous reaction mixture has a molar ratio of water to atomic Si of about 2 to about 80; Element 21: wherein the tetrahedral element is selected from the group consisting of Li, Be, Al, B, P, Si, Ga, Ge, Zn, Cr, Mg, Fe, Co, Ni, Mn, As, In, Sn, Sb, Ti, Zr, and any combination thereof; Element 22: wherein the reaction mixture further comprises a source of hydroxide ions; Element 23: wherein the reaction mixture further comprises a source of halide ions; Element 24: wherein the reaction mixture further comprises an alkali metal / alkaline earth metal ion source; Element 25: wherein the reaction mixture further comprises molecular sieve seeds; Element 26: wherein the reaction is carried out at a temperature of about 75°C to about 200°C; Element 27: wherein the reaction lasts for a period of about 2 hours to about 20 days; Element 28: wherein the molecular sieve has a composition selected from the group consisting of silica, aluminosilicates, borosilicates, aluminoborosilicates, germanosilicates, aluminophosphates and silicoaluminophosphates; Element 29: wherein the molecular sieve has a framework selected from the group consisting of RHO frameworks, LTA frameworks, ITE frameworks, RTH frameworks, ITE / RTH intergrowth frameworks, IWV frameworks, IFW frameworks, *CTH frameworks, SAS frameworks, POS frameworks and MWW frameworks; Element 30: the method further comprises: calcining the molecular sieve at about 500°C to about 900°C; Element 31: the method further comprises: exposing the molecular sieve to an acid; and Element 32: the method further comprises: exposing the molecular sieve to boiling water. Examples of combinations include, but are not limited to, element 18 combined with element 28 and / or element 29; element 18 combined with element 19 and / or element 20; one or more of elements 18-20 combined with element 21; two or more of elements 18-25; a combination of element 26 and / or element 27 with one or more of elements 18-25; a combination of element 28 and / or element 29 with one or more of elements 18-27; and a combination of element 31 and / or element 32 with one or more of elements 18-30.

[0216] A third non-limiting example embodiment of the present disclosure is a composition comprising: an aluminosilicate molecular sieve or an aluminoborosilicate molecular sieve having a RHO framework having a Si to Al ratio greater than or equal to about 8, such as about 8 to about 25. For the aluminoborosilicate molecular sieve, the Si to B ratio may be about 1 to about 25.

[0217] A fourth non-limiting example embodiment of the present disclosure is a composition comprising: a borosilicate molecular sieve having a RHO framework. The borosilicate molecular sieve may have a Si to B ratio of about 1 to about 25 (or about 8 to about 25).

[0218] A fifth non-limiting example embodiment of the present disclosure is a composition comprising: a silica molecular sieve having an IFW framework.

[0219] The sixth non-limiting example embodiment of the present disclosure is a composition comprising: an aluminosilicate molecular sieve having an IFW framework. The aluminosilicate molecular sieve may have a Si to Al ratio of about 3 to about 100 (or about 20 to about 100).

[0220] The seventh non-limiting example embodiment of the present disclosure is a composition comprising: a silica molecular sieve, an aluminosilicate molecular sieve, a borosilicate molecular sieve, an aluminoborosilicate molecular sieve or a germanosilicate molecular sieve having an ITH / RTH intergrowth framework. For aluminosilicate molecular sieves or aluminoborosilicate molecular sieves, the ratio of Si to Al is from about 3 to about 100 (e.g., from about 20 to about 100). For borosilicate molecular sieves or aluminoborosilicate molecular sieves, the ratio of Si to B can be from about 3 to about 100 (or from about 20 to about 100). The composition is a germanosilicate molecular sieve or an aluminoborosilicate molecular sieve having a ratio of Si to Ge of from about 1 to about 100 (or from about 20 to about 100).

[0221] The eighth non-limiting example embodiment of the present disclosure is a composition comprising: a silica molecular sieve or a borosilicate molecular sieve having a *CTH framework, which may not contain Ge. The ratio of Si to B may be from about 4 to about 25.

[0222] A ninth non-limiting example embodiment of the present disclosure is a composition comprising: a silicoaluminophosphate molecular sieve having a SAS framework. The ratio of Si to Al may be about 1 to about 25.

[0223] Unless otherwise indicated, all numerical values ​​used in the specification and the appended claims to express quantities of ingredients, properties such as molecular weight, reaction conditions, etc., should be understood in all cases as being modified by the term "about". Therefore, unless otherwise indicated, the numerical parameters listed in the following specification and the appended claims are approximate values, which may vary depending on the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0224] One or more illustrative embodiments incorporating the invention embodiments disclosed herein are presented herein. For the sake of clarity, all features of physical implementation are not described or shown in this application. It should be understood that in the development of the physical implementation incorporating the invention embodiments, many execution-specific decisions must be made to realize the developer's goal, such as complying with system-related, business-related, government-related and other constraints, which depend on implementation and change from time to time. Although the efforts of the developers may be time-consuming, for those of ordinary skill in the art, this effort remains a routine task and benefits from the present disclosure.

[0225] Although compositions and methods are described herein in terms of "comprising" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components and steps.

[0226] In order to help better understand the embodiments of the present invention, the following examples of preferred or representative embodiments are given. The following examples should not be interpreted as limiting in any way, or defining the entire scope of the present invention. Example

[0227] Example 1. Reaction Scheme 1 shows the synthesis of Compound X (SDA embodiment of Compound V). 200 mL of anhydrous THF was cannulated into a 500 mL flame-dried round-bottom flask with a stirring bar. 3.965 g (30.0 mmol) of 2-methylbenzimidazole was added to the flask, which was then purged with nitrogen. The reaction mixture was cooled to -78°C. 12.0 mL (30.0 mmol, 1.0 eq) of 2.5 M n-butyl lithium was added to the reaction mixture and stirred at -78°C for 5 minutes, then returned to room temperature and stirred at room temperature for 15 minutes. 12.77 g (90.0 mmol, 3.0 eq) of iodomethane was added and the reaction was stirred at room temperature for 16 hours. The light brown reaction mixture was poured into 150 ml of deionized water, extracted twice with 75 ml of ethyl acetate and twice with 75 ml of dichloromethane. The combined organic layer was dried over sodium sulfate, gravity filtered into a pre-weighed round-bottom flask, and the solvent was removed by vacuum to obtain the product, which was a beige solid (3.04g, 69.3% yield). 7.52g (51.2mmol, 2.05 equivalents) of the product from the previous reaction was placed in a 500-mL round-bottom flask with a stirring rod and dissolved in 100mL acetonitrile. 5.74g 1,5-dibromopentane (24.97mmol, 1.0 equivalent) was added to the flask, and the reaction was refluxed under nitrogen for 72 hours. White solid was precipitated in the reaction mixture. The precipitate was filtered on a medium frit and washed 3 times with 50mL acetone. The solid was placed in an evaporating dish and dried overnight in a vacuum oven to produce 10.15g. (yield 78.0%).

[0228] Reaction Scheme 1

[0229]

[0230] (Acetonitrile is acetonitrile)

[0231] The synthesis of compounds Y and Z can be carried out similarly. For example, to prepare compound Y, 1,5-dibromopentane is replaced with 1 molar equivalent of 1,4-dibromobutane.

[0232]

[0233] Where X - It is bromine -

[0234]

[0235] Where X - It is bromine -

[0236] Example 2.In a 1.5 mL reactor, boric acid, tetramethyl orthosilicate (TMOS), and a hydroxide solution of compound X were combined with sufficient water to provide a molar ratio of atomic Si to atomic B of 10 and a molar ratio of atomic Si to SDA of 4 in the reaction mixture. The mixture was then freeze-dried to remove methanol and most of the water, and then the molar ratio of water to atomic Si was adjusted to 4 by back-adding deionized water. The reaction mixture was heated at 150° C. for 10 days to produce a mixture of borosilicate Rho molecular sieves and amorphous material. Figure 3 is a scanning electron microscope (SEM) micrograph of the product.

[0237] Example 3. The reaction mixture of Example 2 was heated at 150°C for a total of 28 days to produce substantially pure borosilicate Rho molecular sieve (less than 2 wt% amorphous product).

[0238] Example 4. The conditions of Example 2 were reproduced in a Steel Parr reactor with a 10 mL Teflon insert, with the addition of seeds from the product of Example 3. The seeds increased the reaction rate, resulting in substantially pure borosilicate Rho molecular sieves within 11 days. Figures 4A-4D is a SEM micrograph of the product.

[0239] The product of Example 4 was calcined in a box furnace in a staged procedure. The sample was exposed to flowing nitrogen at room temperature for two hours, and then the temperature was ramped from room temperature to 400°C over two hours while being maintained under a nitrogen flow. The temperature was then held at 400°C for 15 minutes, and then the atmosphere was switched from flowing nitrogen to flowing dry air. The temperature was then ramped from 400°C to 600°C over 1 hour. The temperature was maintained at 600°C for 16 hours, and then the box furnace was cooled. Unless otherwise stated, this is the method for calcining the other examples described herein.

[0240] Calcination removes SDA from the borosilicate Rho molecular sieve. Figure 5 Tables 11 and 12 are XRD patterns of the as-produced borosilicate Rho molecular sieve and the calcined borosilicate Rho molecular sieve, respectively (Bruker Davinci D8 Discovery Instrument, in continuous mode, using Cu Kα radiation; Bragg-Bentano geometry, with Vantec 500 detector; angle range: 2-θ of 4° to 36°). The as-produced borosilicate Rho molecular sieve has an α parameter of The calcined borosilicate Rho molecular sieve has an α of Unlike other typical Rho molecular sieves, the borosilicate Rho molecular sieve of the present invention having a higher silica content shows little change in the unit cell when the occluded material is removed.

[0241] Table 11

[0242]

[0243] Table 12

[0244]

[0245] Example 5. Example 3 The synthesis was repeated in a 23 ml Parr bomb. Thermogravimetric analysis (TGA) was performed on the as-produced borosilicate Rho molecular sieve in air. There was a cumulative mass loss of 23.7 wt% up to 800°C, indicating the removal of SDA and water.

[0246] The product of Example 5 was calcined as described in Example 4. After calcination, the product was allowed to stand overnight in the open air. TGA was performed on the calcined borosilicate Rho molecular sieve in air. The cumulative mass loss up to 400°C was less than 6 wt %, which is a high temperature sufficient to remove adsorbed water. The low wt % loss observed indicates that the calcined borosilicate Rho molecular sieve adsorbs very little water and that the hydrophilicity of the calcined borosilicate Rho molecular sieve is lower than that of a typical Rho molecular sieve with a lower siliceous content.

[0247] BET analysis of nitrogen adsorption data showed that the surface area and micropore volume of the calcined borosilicate Rho molecular sieve were 993 m 2 / g and 0.37cm 3 / g.

[0248] Example 6. Ultrasil TM Example 5 (seed synthesis) was repeated as silica source and only 10 days of reaction time. The borosilicate Rho molecular sieve produced had only trace amounts of amorphous product (less than 1 wt% amorphous product). Fig. 6A and 6B is a SEM micrograph of the product.

[0249] Example 7. Use LUDOX TM Example 5 (seed synthesis) was repeated with LS-30 (available from Du Pont) as the silica source and only 10 days of reaction time. The borosilicate Rho molecular sieve produced was pure Rho (less than 0.1 wt% amorphous product). Figure 7 is a SEM micrograph of the product.

[0250] Example 8. Example 4 (seed synthesis) was repeated using TMOS as the silica source, a water to atomic Si molar ratio in the reaction mixture of 7, and a reaction time of only 7 days. The borosilicate Rho molecular sieve produced was pure Rho. Fig. 8A and 8B is a SEM micrograph of the product.

[0251] Example 9. In the table and below, unless otherwise stated, the synthesis was carried out in a 1.5-mL well of a parallel reactor synthesis reactor. Each of the syntheses used a stainless steel liner with steel balls. Several aluminosilicate Rho molecular sieves and borosilicate Rho molecular sieves were prepared using compound Y as the SDA and according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 13. Please specify which SDA was used - different from the SDA above. The boron source was 3.47 wt % boric acid in water. The potassium source was 17.54 wt % KOH in water. The sodium source was 2 wt % to 10 wt % NaOH in water. The reaction temperature was 160°C.

[0252] Table 13

[0253]

[0254] a L is for LUDOX TM LX-30 (30 wt% SiO2); A is AERODISP TM W7330N (30 wt% SiO2).

[0255] b Aluminum source is USALCO TM LSA (8.86 wt % in water).

[0256] c The source of aluminum is kaolin.

[0257] Example 10. Several aluminophosphate LTA molecular sieves and silicoaluminophosphate LTA molecular sieves were prepared according to the reaction mixture components and relative concentrations and product descriptions provided in Table 14. The alumina source was 69.3 wt% CATAPAL in water. TM A (aluminium hydroxide, available from Sasol). The phosphorus source was 50 wt% phosphoric acid in water. The reaction time was 4 days and the reaction temperature was 160°C.

[0258] Table 14

[0259]

[0260] a T is the total number of moles of aluminum, phosphorus and silicon atoms in the reaction mixture.

[0261] b L is for LUDOX TM LS-30 (30 wt% SiO2); A is AERODISP TM W7330 (30 wt% SiO2).

[0262] c The source of magnesium cations is magnesium nitrate; the source of nickel cations is nickel nitrate.

[0263] Example 11. The molecular sieve was prepared using compound Y as SDA, a molar ratio of SDA to Si of 0.125, a molar ratio of tetramethylammonium hydroxide to Si of 0.25, and a molar ratio of F to Si of 0.5. The synthesis was carried out at 150°C for 8 days. The molecular sieve product obtained was about 60 wt% LTA and 40 wt% AST.

[0264] Example 12. Compound AA was prepared by adding 14.8 g of 2,3-lutidine and 25.0 g of 1-bromo-3-phenylpropane to a 125-mL Teflon insert. To this was added 60 mL of acetonitrile solvent. The liner was then capped and placed inside a 125-mL Parr steel autoclave, which was then heated at 90 °C for 16 hours. The autoclave was removed and cooled to room temperature. The solvent was then removed from the mixture by rotary evaporation, and the solid residue was washed with ether to remove unreacted reagents. After the solid was air-dried, the overall yield was 95%. 1 H and 13 C NMR verifies product purity. The compound is converted to its hydroxide form in a batch reaction by dissolving it in deionized water and adding it to a 3-fold excess of Dowex anion exchange resin. After about 12 hours, the solution is separated by filtration and the resin is washed with deionized water. The combined aqueous fractions are then concentrated in a rotary evaporator to obtain a 15.7 wt % solution, determined by titration with 0.1 M HCl solution.

[0265]

[0266] Several aluminosilicate and borosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 15. SDA is a molecular sieve having OH - Counterion Compound AA (embodiment of Compound E).

[0267] Table 15

[0268]

[0269]

[0270] a L is for LUDOX TM HS-30 (30 wt% SiO2); A is AERODISP TM W7330 (30 wt% SiO2).

[0271] b S is 8.86% sodium aluminate solution, B is 3.47% boric acid solution, M is MS-25 amorphous silica / alumina (65.5% silica-22% alumina), and Y is USY zeolite (Si / Al=3.05).

[0272] c The reaction mixture also contained NaOH with a Na:Si ratio of 0.10.

[0273] d The reaction mixture also contained NaOH with a Na:Si ratio of 0.20.

[0274] Fig. 9 The XRD patterns of Example 12.22 (aluminosilicate Rth molecular sieve, upper figure) and Example 12.5 (borosilicate Rth molecular sieve, lower figure) are plotted.

[0275] The synthesis of sample 12.14 was repeated on a larger scale in a 23 mL steel Parr autoclave, but with a Si to Al molar ratio of 20 instead of 40. After heating at 160 °C for 17 days, a pure RTH-type phase was obtained. Fig.10 Table 16 provides the peak positions of the XRD patterns. Fig.11A and 11B is a SEM micrograph of the product.

[0276] Table 16

[0277]

[0278]

[0279] In addition, several aluminosilicate, borosilicate and germanosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions and product descriptions provided in Table 17. The silica source was TMOS. SDA was a - The counter ion of the compound is AA.

[0280] Table 17

[0281]

[0282] a B is 3.47% boric acid solution, N is aluminum nitrate, and G is germanium oxide.

[0283] b The reaction mixture included ITQ-24 seeds.

[0284] c The reaction mixture included ITQ-33 seeds.

[0285] L = Lamellar phase

[0286] Example 13. Several aluminosilicate and borosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 18. SDA is a molecular sieve having OH - Compound AB of the Counterion (Embodiment of Compound E). Compound AB was prepared in a similar manner to Compound AA, except that an equimolar amount of 2,3,5-trimethylpyridine was used instead of 2,3-lutidine.

[0287]

[0288] Table 18

[0289]

[0290] a L is for LUDOX TM HS-30 (30 wt% SiO2); A is AERODISP TM W7330 (30 wt% SiO2).

[0291] b S is 8.86% sodium aluminate solution, B is 3.47% boric acid solution, M is MS-25, MK is metakaolin, K is potassium aluminate, and Y is Y-type molecular sieve.

[0292] c The reaction mixture included ITQ-21 seeds.

[0293] d The reaction mixture included ITQ-24 seeds.

[0294] e The reaction mixture included ITQ-33 seeds.

[0295] f The ratio of Si:Ti is 100, anatase.

[0296] Table 19 provides the peaks of the XRD pattern of Sample 13.9.

[0297] Table 19

[0298]

[0299] The synthesis of sample 13.9 was repeated on a larger scale in a 45-mL steel Parr autoclave except that seeds of the ITE molecular sieve from sample 13.9 were used. To a 45-mL Teflon insert were added 11.1 g of SDAOH solution ([OH] = 0.90 mmol / g), 5.6 g of LUDOX TM LS-30 colloidal silica, 7.9 g distilled water, 0.37 g MS-25, 19 mg ITQ-33 seeds and 20 mg sample 13.9 seeds. The liner was then capped, sealed in a 45-ml steel Parr autoclave and placed in an oven with a rotary spitter. The reactor was tumbled at about 30 rpm. After heating at 160° C. for 7 days, a pure ITE-type phase molecular sieve was obtained. Fig.12 is the XRD pattern of the obtained product, and Table 20 provides the peaks of the XRD pattern. Fig.13A and 13B is a SEM micrograph of the obtained product.

[0300] Table 20

[0301]

[0302]

[0303] The above scaled-up synthesis using the sample 13.9 seed was repeated, but without the seed crystals. After 12 days, a pure ITE-type phase molecular sieve was obtained.

[0304] In addition, several aluminosilicate, borosilicate and germanosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions and product descriptions provided in Table 21. The silica source was TMOS. SDA was a - Counter ion of compound AB.

[0305] Table 21

[0306]

[0307] a N is aluminum nitrate, G is germanium oxide, and B is 3.47% boric acid solution.

[0308] b The reaction mixture included ITQ-33 seeds.

[0309] Example 14.The random intergrowth framework of ITE / RTH was prepared by using a mixture of template SDA molecules selective for ITE or RTH frameworks, respectively. 2.78 g of SDA solution compound AB ([OH] = 0.90 mmol / g), 3.78 g of SDA solution compound AA ([OH] = 0.66 mmol / g) and 2.94 g of deionized water were added to a 23 mL Teflon insert. 2.80 g of LUDOX TM LS-30 and 0.185 g MS-25 amorphous silica / alumina. The liner was then capped, sealed in a 23-ml steel Parr autoclave and placed in an oven with a rotary spit. The reactor was tumbled at about 30 rpm. After heating at 160°C for 7 days, an ITE / RTH intergrowth phase was obtained. Fig.14 The X-ray powder patterns of the intergrowth were compared to those of the pure RTH and ITE framework products of the previous examples. The broadening of specific features in the patterning is consistent with the simulations of Wagner et al.

[0310] Example 15. According to the reaction mixture components and reaction conditions provided in Table 22, a - Compound AC (an embodiment of Compound E) with a counterion as SDA produced a borosilicate product having a mixture of IFW and IWV type phases. The silica source was LUDOX TM HS-30 (30 wt% SiO2). The boron source was 3.47% boric acid solution. Compound AC was prepared in a similar manner to Compound AA, except that 2,4-lutidine was used instead of 2,3-lutidine.

[0311]

[0312] Table 22

[0313]

[0314] Example 16. Several germanosilicate LTA molecular sieves were prepared according to the reaction mixture components, reaction conditions and product descriptions provided in Table 23. The silicon dioxide source was TMOS. The germanium source was germanium oxide. SDA was compound Z.

[0315] Table 23

[0316]

[0317] Example 17. According to the reaction mixture components and reaction conditions provided in Table 24, a -Compound AD (embodiment of compound J) with counter ions was used as SDA to prepare silicoaluminophosphate molecular sieves. The silica source was LUDOX TM LS-30. Alumina source is CATAPAL TM A.

[0318] The phosphorus source was phosphoric acid and the reaction time was 4 days at 160°C.

[0319]

[0320] Table 24

[0321]

[0322] a T is the molar sum of aluminum, phosphorus and silicon atoms.

[0323] Example 18. Several aluminosilicate and borosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 25. SDA is a molecular sieve having OH - Compound AD with counter ion.

[0324] Table 25

[0325]

[0326]

[0327] a L is for LUDOX TM HS-30 (30 wt% SiO2); A is AERODISP TM W7330 (30 wt% SiO2).

[0328] b S is 8.86% sodium aluminate solution, B is 3.47% boric acid solution, M is MS-25, MK is metakaolin, K is potassium aluminate, and Y is Y-type molecular sieve.

[0329] c The reaction mixture included ITQ-33 seeds.

[0330] c The reaction mixture included ITQ-21 seeds.

[0331] d The reaction mixture included ITQ-24 seeds.

[0332] e The Si:Ti ratio is 39, anatase.

[0333] Repeat the synthesis of sample 17.4, but use a seed and a KOH to Si ratio of 0.15, a Si to Al ratio of 40, a Si to B ratio of 24, a SDAOH to Si ratio of 0.30, and a H2O to Si ratio of 32. To a 23 mL Teflon insert was added 4.15 g of SDAOH solution (1.085 mmol / g) and 2.25 g of 1 N KOH. To this was added 0.035 g of aluminum hydroxide (Aldrich) and 0.04 g of boric acid, which were dissolved by stirring. To this solution was then added 3.00 g of AERODISP TM W7330N colloidal silica (30%) and about 0.02 g of seed from sample 17.4. The liner was then capped, sealed in a 23 mL steel Parr autoclave and placed in an oven with a rotary spit. The reactor was tumbled at about 30 rpm. After heating at 160° C. for 5 days, an IFW-type phase was obtained without any layered silicate or quartz impurities. Fig.15A and 15B is a SEM micrograph of the product.

[0334] The previous synthesis using the seeds from sample 17.4 was repeated, but using (a) a higher aluminum concentration (Si to Al ratio of 25), (b) a lower boron concentration (Si to B ratio of 40), and (c) 0.02 g of seeds of the previous product (corresponding to Fig.15A and 15B ), instead of sample 17.4 seed. After 6 days, a pure IFW-type phase was obtained. Fig.16 is the XRD pattern of the product, and Table 26 is the peaks of the XRD pattern of the product. Fig.17A and 17B The XRD patterns of sample 17.10 (borosilicate IFW molecular sieve, upper figure) and the aluminosilicate IFW molecular sieve (lower figure) are plotted. Fig. 17B yes Fig.17A A zoomed-in version of the 100 nm quartz crystals clearly shows the different peak positions for the different compositions. These are the first demonstrations of the direct synthesis of aluminosilicate IFW-type molecular sieves.

[0335] Table 26

[0336]

[0337]

[0338] The previous synthesis using seeds from sample 17.4 was repeated, but using (a) a higher aluminum concentration (Si to Al ratio of 25), (b) no boron source, and (c) 0.02 g of seeds of the previous product (corresponding to Fig.15A and 15B ), instead of the sample 17.4 seed. After 6 days, a pure IFW-type phase without boron was obtained.

[0339] In addition, IFW and RTH borosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 27. The silica source was TMOS. The boron source was a 3.47% boric acid solution. SDA was Compound AD described above. The reaction time was 10 days at 150°C.

[0340] Table 27

[0341]

[0342]

[0343] Example 19. Several germanosilicate IWV molecular sieves were prepared according to the reaction mixture components, reaction conditions and product descriptions provided in Table 28. The silicon dioxide source was TMOS. The germanium source was germanium oxide. SDA was a - Compounds AE of the counterion (embodiment of Compound E).

[0344]

[0345] Table 28

[0346]

[0347] The XRD pattern peaks for Sample 18.2 are provided in Table 29.

[0348] Table 29

[0349]

[0350]

[0351] Example 20. Several aluminosilicate and borosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 30. SDA is a molecular sieve having OH - Compounds AF of the counterion (embodiment of Compound F).

[0352]

[0353] Table 30

[0354]

[0355]

[0356] a L is for LUDOX TM HS-30 (30 wt% SiO2); A is AERODISP TMW7330 (30 wt% SiO2).

[0357] b MK is metakaolin, B is 3.47% boric acid solution, and K is potassium aluminate.

[0358] Additionally, aluminosilicate, borosilicate, and germanosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions, and product descriptions provided in Table 31. The silica source was TMOS. The boron source was 3.47% boric acid solution. The aluminum source was aluminum nitrate. SDA was Compound AF.

[0359] Table 31

[0360]

[0361] a The reaction mixture included ITQ-24 seeds.

[0362] b The reaction mixture included ITQ-33 seeds.

[0363] The XRD pattern peaks for Sample 19.20 are provided in Table 32.

[0364] Table 32

[0365]

[0366] Example 21. Germanosilicate molecular sieves were prepared according to the reaction mixture components, reaction conditions and product descriptions provided in Table 33. The silicon dioxide source was TMOS. The germanium source was germanium oxide. SDA was a hydroxyl group having OH - Compound AG with counter ion.

[0367]

[0368] Table 33

[0369]

[0370] In this example, the product is a material with a POS framework, i.e., a material with a 12×11×11 ring structure in which the channels intersect to create a large cavity. This material is isostructural with PKU-16 (a germanosilicate structure with 11×11×12 ring channels solved by "electron crystallography", Angew. Chem. Int. Ed., 53, 5868-5871 (2014)).

[0371] Therefore, the present invention is fully suitable for obtaining the objects and advantages mentioned and those inherent therein. The specific embodiments disclosed above are illustrative only, because the present invention can be modified and practiced in different but equivalent ways that are obvious to those skilled in the art who benefit from the teachings herein. In addition, except as described in the claims below, there is no intention to limit the details of the construction or design shown herein. Therefore, it is obvious that the specific illustrative embodiments disclosed above can be changed, combined or modified, and all such variations are considered to be within the scope and spirit of the present invention. The present invention disclosed illustratively herein can be properly practiced in the absence of any element not specifically disclosed herein and / or any non-essential element disclosed herein. Although compositions and methods are described according to "comprising", "containing" or "including" various components or steps, the compositions and methods can also be "essentially composed of" the various components and steps or "composed of" the various components and steps. All numbers and ranges disclosed above can vary by a certain amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are clearly disclosed. In particular, each range of values ​​disclosed herein (in the form of "from about a to about b" or equivalently "from approximately a to b" or equivalently "from approximately ab") should be understood to list each number and range encompassed in the broader range of values. In addition, the terms in the claims have their ordinary normal meaning unless otherwise explicitly and clearly defined by the patentee. In addition, the indefinite articles "a" or "an" used in the claims are defined herein to mean one or more of the elements they introduce.

[0372] All priority documents are fully incorporated herein by reference to the extent such incorporation is permitted. In addition, all documents (including test procedures) cited herein are fully incorporated herein by reference to the extent such incorporation is permitted.

Claims

1. A method for preparing a molecular sieve, comprising: Make the tetrahedral element source in the selected Ar + -L-Ar, Ar + -L-Ar-L-Ar + and Ar + -L-Ar-L-NR3 + ,ArAr + -L-Ar + Ar and a mixture thereof in the presence of a structure directing agent SDA to produce a molecular sieve, wherein Ar + refers to a cationic aromatic ring containing N, Ar refers to an uncharged aromatic ring, ArAr + and Ar + Ar is a fused aromatic ring structure containing both a N-containing cationic moiety and an uncharged moiety, L is a methylene chain of 3 to 6 carbon atoms, and NR3 + refers to quaternary ammonium, The molecular sieve has a framework selected from the group consisting of an RHO framework, an LTA framework, an ITE framework, an RTH framework, an ITE / RTH symbiotic framework, an IWV framework, an IFW framework, a *CTH framework, a SAS framework, a POS framework and an MWW framework.

2. The method for preparing a molecular sieve according to claim 1, wherein the cationic aromatic ring containing N is selected from: pyridine Substituted pyridine Imidazole Substituted Imidazole Pyrazole Substituted pyrazoles Pyrazine Substituted pyrazines Pyrimidine and substituted pyrimidines and wherein the uncharged aromatic ring is selected from the group consisting of: phenyl, substituted phenyl, naphthyl, and substituted naphthyl.

3. The method for preparing a molecular sieve according to claim 1, wherein the SDA has the formula Ar + -L-Ar, where Ar + It is an optionally substituted pyridine Ar is an optionally substituted phenyl group, and L is a methylene chain of 3 to 6 carbon atoms.

4. The method for preparing a molecular sieve according to claim 3, wherein the SDA is selected from: Where R1-R 10 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl; and wherein N + OH - 、F - , Cl - Br - or I - balance.

5. The method for preparing a molecular sieve according to claim 4, wherein R1-R5 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and R6-R 10 Each is H.

6. The method for preparing a molecular sieve according to claim 1, wherein the SDA has the formula Ar + -L-Ar, where Ar + It is an optionally substituted imidazole Ar is an optionally substituted phenyl group, and L is a methylene chain of 3 to 6 carbon atoms.

7. The method for preparing a molecular sieve according to claim 6, wherein SDA is selected from: Where R2-R 10 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and wherein N + OH - 、F - , Cl - Br - or I - balance.

8. The method for preparing a molecular sieve according to claim 7, wherein R2-R5 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and R6-R 10 Each is H.

9. The method for preparing a molecular sieve according to claim 1, wherein the SDA has the formula Ar + -L-Ar-L-Ar + , where Ar + It is an optionally substituted pyridine Ar is an optionally substituted phenyl group, and L is a methylene chain of 3 to 6 carbon atoms.

10. The method for preparing a molecular sieve according to claim 9, wherein SDA is selected from: wherein R1-R4 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and R6-R 10 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and wherein N + OH - 、F - , Cl - Br - or I - balance.

11. The method for preparing a molecular sieve according to claim 10, wherein R1-R4 are each H, and R6-R 10 and R is independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl.

12. The method for preparing a molecular sieve according to claim 1, wherein the SDA has the formula Ar + -L-Ar-L-Ar + , where Ar + It is an optionally substituted imidazole Ar is an optionally substituted phenyl group, and L is a methylene chain of 3 to 6 carbon atoms.

13. The method for preparing a molecular sieve according to claim 12, wherein SDA is selected from: wherein R2-R9 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and wherein N + OH - 、F - , Cl - Br - or I - balance.

14. The method for preparing a molecular sieve according to claim 13, wherein R2-R5 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and R6-R9 are each H.

15. The method for preparing a molecular sieve according to claim 1, wherein the SDA has the formula Ar + -L-Ar-L-NR3 + , where Ar + It is an optionally substituted pyridine Ar is an optionally substituted phenyl group, and L is a methylene chain of 3 to 6 carbon atoms, and NR3 + It is a quaternary ammonium.

16. The method for preparing a molecular sieve according to claim 15, wherein SDA is selected from: wherein R1-R4 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and R6-R 13 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl; and wherein N + OH - 、F - , Cl - Br - or I - balance.

17. The method for preparing a molecular sieve according to claim 16, wherein R1-R4 are each H; R6-R 10 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl; and R 11 -R 13 Each is CH3.

18. The method for preparing a molecular sieve according to claim 1, wherein the SDA has the formula ArAr + -L-Ar + Ar + , where Ar + Ar + andArAr + It is an optionally substituted benzimidazole and L is a methylene chain of 3-6 carbon atoms.

19. The method for preparing a molecular sieve according to claim 18, wherein SDA is selected from: wherein R2-R3 are independently H, C1-C6 branched or linear alkyl or C5-C6 cycloalkyl, and wherein N + OH - 、F - , Cl - Br - or I - balance; and any combination thereof.

20. The method for preparing a molecular sieve of any one of claims 1-19, wherein the tetrahedral elements include Si; and wherein the aqueous reaction mixture has a molar ratio of atomic Si to structure directing agent of 1 to 20, and wherein the aqueous reaction mixture has a molar ratio of water to atomic Si of 2 to 80.

21. The method for preparing a molecular sieve according to any one of claims 1 to 19, wherein the tetrahedral element source is selected from the group consisting of a silicon source, a germanium source, an aluminum source, a boron source, a phosphorus source, and any combination thereof.

22. The method for preparing a molecular sieve according to claim 20, wherein the aqueous reaction mixture further comprises at least one of the following: a hydroxide ion source, a halide ion source, an alkali metal / alkaline earth metal ion source, and a molecular sieve seed crystal.

23. The method for preparing a molecular sieve according to any one of claims 1 to 19, wherein the reaction is carried out at a temperature of 75°C to 200°C.

24. The method for preparing a molecular sieve according to any one of claims 1 to 19, wherein the molecular sieve has a composition selected from the group consisting of silicon dioxide, aluminosilicates, borosilicates, aluminoborosilicates, germanosilicates, aluminophosphates, silicoaluminophosphates and metalloaluminophosphates.

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