Methods of making EMM-73 molecular sieves, EMM-73 molecular sieves obtained therefrom, and uses thereof

Abstract

The present disclosure relates to methods of making EMM-73 molecular sieves. The present disclosure also relates to EMM-73 molecular sieves obtained therefrom, including EMM-73 molecular sieves of high Y / X molar ratio, small crystal forms EMM-73 molecular sieves and uses thereof. The EMM-73 molecular sieves can be made in hydroxide media or fluoride media.

Description

METHODS OF MAKING EMM-73 MOLECULAR SIEVES, EMM-73 MOLECULAR SIEVES OBTAINED THEREFROM, AND USES THEREOFHELD OF THE INVENTION

[0001] The present disclosure relates to methods of making EMM-73 molecular sieves. The present disclosure also relates to EMM-73 molecular sieves obtained therefrom, including EMM-73 molecular sieves of high Y / X molar ratio and small crystal forms EMM-73 molecular sieves and uses thereof.BACKGROUND OF THE INVENTION

[0002] Molecular sieve materials, both natural and synthetic, may be used as adsorbents and have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AlPOs, and mesoporous materials, are ordered, porous crystalline materials having a definite crystalline structure as determined by X-ray diffraction (XRD). Certain molecular sieves are ordered and produce specific identifiable XRD patterns. Within certain molecular sieve materials there may be a large number of cavities, which may be interconnected by a number of channels or pores. These cavities and pores are uniform in size within a specific molecular sieve material. Because the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of industrial processes, e.g., cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0003] Molecular sieves that find application in catalysis and adsorption include any of the naturally occurring or synthetic crystalline molecular sieves. These zeolites and their isotypes are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, framework type zeolites and other crystalline microporous molecular sieves, for which a structure has been established, are assigned a three letter code and are described in the “Atlas of Zeolite Framework Types”, eds. Ch. Baerlocher, L.B. McCusker, and D.H. Olson, Elsevier, Sixth Edition, 2007, which is hereby incorporated by reference. These zeolites and their isotypes are also described in http: / / america.iza-structure.org / IZA-SC / ftc_table.php.

[0004] The idealized inorganic framework structure of zeolites is a framework of silicate in which all tetrahedral atoms are connected by oxygen atoms with the four next-nearest tetrahedral atoms. The term “silicate”, as used herein, refers to a substance containing at leastsilicon and oxygen atoms that are alternately bonded to each other ( / .<?., -O-Si-O-Si-), and optionally including other atoms within the inorganic framework structure, including atoms such as boron, aluminum, or other metals (e.g., transition metals, such as titanium, vanadium, or zinc). Atoms other than silicon and oxygen in the framework silicate occupy a portion of the lattice sites otherwise occupied by silicon atoms in an ‘all-silica’ framework silicate. Thus, the term “framework silicate” as used herein refers to an atomic lattice comprising any of a silicate, borosilicate, gallosilicate, ferrisilicate, aluminosilicate, titanosilicate, zincosilicate, vanadosilicate, or the like.

[0005] The structure of the framework silicate within a given zeolite determines the size of the pores or channels that are present therein. The pore or channel size may determine the types of processes for which a given zeolite is applicable. Currently, greater than 200 unique zeolite framework silicate structures are known and recognized by the Structure Commission of the International Zeolite Association, thereby defining a range of pore geometries and orientations.

[0006] The framework silicates of zeolites or molecular sieves are commonly characterized in terms of their ring size, wherein the ring size refers to the number of silicon atoms (or alternative atoms, such as those listed above) that are tetrahedrally coordinated with oxygen atoms in a loop to define a pore or channel within the interior of the zeolite. For example, an “8-ring” zeolite refers to a zeolite having pores or channels defined by 8 alternating tetrahedral atoms and 8 oxygen atoms in a loop. The pores or channels defined within a given zeolite may be symmetrical or asymmetrical depending upon various structural constrains that are present in the particular framework silicate.

[0007] Zeolites can be classified as having small, medium, large, and extra-large pore structures for pore windows delimited by 8, 10, 12, and more than 12 T-atoms, respectively. Extra-large pore zeolites (>12R) include, for example, AET (14R, e.g., ALPO-8), SFN (14R, e.g., SSZ-59), VFI (18R, e.g., VPI-5), CLO (20R, e.g., cloverite), and ITV (30R, e.g., ITQ-37) framework type zeolites. Extra-large pore zeolites generally have a free pore diameter of larger than about 0.8 nm. Large pore zeolites (12R) include, for example, LTL, MAZ, FAU, EMT, OFF, MTW, *BEA, MOR, BOG, and SFS framework type zeolites, e.g., mazzite, offretite, zeolite L, zeolite Y, zeolite X, omega, ZSM-2, ZSM-12, zeolite T, Beta, boggsite, and SSZ-56. Large pore zeolites generally have a free pore diameter of 0.6 to 0.8 nm. Medium (or intermediate) pore size zeolites (10R) include, for example, MFI, MEL, *MRE, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites, e.g., ZSM-5, ZSM- II, ZSM-48, ZSM-22, ZSM-23, ZSM-35, MCM-22, silicalite- 1 , and silicalite-2. Medium poresize zeolites generally have a free pore diameter of 0.45 to 0.6 nm. Small pore size zeolites (8R) include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework type zeolites, e.g. , ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, and ALPO-17. Small pore size zeolites generally have a free pore diameter of 0.3 to 0.45 nm.

[0008] Synthesis of zeolite materials typically involves hydrothermal crystallization from a synthesis mixture comprising sources of all the elements present in the zeolite such as sources of silica but also of alumina etc. In many cases a structure directing agent (SDA) is also present. Structure directing agents are compounds which are believed to promote the formation of zeolites (or molecular sieves) and which are thought to act as templates around which certain zeolites (or molecular sieve structures) can form and which thereby promote the formation of the desired molecular sieve. Various compounds have been used as structure directing agents including various types of quaternary ammonium cations. Typically, zeolite (or molecular sieve) crystals form around structure directing agents with the structure directing agent occupying pores in the zeolite (or molecular sieve) once crystallization is complete. The “as- synthesized” (or “as-made”) zeolite (or molecular sieve) will therefore contain the structure directing agent in its pores so that, following crystallization, the “as-synthesized” zeolite (or molecular sieve) is usually subjected to a treatment step such as a calcination step to remove the structure directing agent.

[0009] Examples of molecular sieves of SFS framework type, characterized by a two- dimensional channel system of intersecting 10-ring and 12-ring pores (12MRxlOMR zeolite), include SSZ-56 and EMM-73 molecular sieves. Synthesis of plate-like borosilicate and needlelike aluminosilicate SSZ-56 was disclosed in e.g., US2006 / 0292071, US2007 / 0034549, US2020 / 0062605, and US2013 / 0330272. WO2023 / 168174 discloses EMM-73 molecular sieves and their preparation using benzimidazolium and 4,5,6,7-tetrahydrobenzimidazolium cations as structure directing agents. As detailed in WO2023 / 168174, EMM-73 has a similar powder XRD patterns to SSZ-56 molecular sieves in terms of degree 2-theta and d-spacing but with different relative intensities.

[0010] Despite these advances, there remains a need for more efficient methods for the synthesis of molecular sieves, such as molecular sieves of SFS framework type, e.g., EMM-73 molecular sieve.SUMMARY OF THE INVENTION

[0011] In a first aspect, the present disclosure relates to a method of making EMM-73 molecular sieve in hydroxide media, comprising the following steps:(a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of hydroxide ions (OH), and optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4- azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III:Formula III where R is selected from methyl, ethyl, and n-propyl, R’ is selected from methyl, ethyl and n- propyl, and n is 4 to 10, and wherein, if Y is Si, X is Al, the structure directing agent (Q) is 1,5 -diethyl-5 -azaindolium or 1- propyl-5-methyl-5-azaindolium, and in the absence of seed crystals, an alkali and / or alkaline earth metal element (M) is present in a M / OH molar ratio of more than 0.5;(b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve;(c) recovering at least a portion of the molecular sieve from step (b); and(d) optionally treating the molecular sieve recovered in step (c) to remove at least part of thestructure directing agent (Q).

[0012] In a second aspect, the present disclosure relates to a method of making EMM-73 molecular sieve in fluoride media, comprising the following steps:(a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), optionally a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, 5-azaindolium monoquaternary cations of Formula II, and 5-azaindolium diquaternaryFormula I Formula IIFormula III where R is selected from methyl, ethyl, and n-propyl, in Formula I R’ is selected from methyl, ethyl and n-propyl, in Formula II R’ is methyl or n-propyl, and n is 4, 5, 7, 9 or 10,(b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve;(c) recovering at least a portion of the molecular sieve from step (b); and(d) optionally treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

[0013] In a third aspect, the present disclosure relates to an EMM-73 molecular sievehaving at least one of 4-azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III as defined above within its pore structure.

[0014] In a fourth aspect, the present disclosure relates to an EMM-73 molecular sieve obtainable by (or obtained by) the methods disclosed herein.

[0015] In a fifth aspect, the present disclosure therefore relates to an EMM-73 molecular sieve characterized by a Y / X molar ratio of more than 100, for instance higher than 100 to 500, e.g, higher than 100 to 250, as determined by ICP elemental analysis.

[0016] In a sixth aspect, the present disclosure relates to an EMM-73 molecular sieve, advantageously an aluminosilicate or a boroaluminosilicate EMM-73 molecular sieve, characterized by a maximal particle size and / or an average maximal particle size of less than 100 nm, such as less than 75 nm or even of less than 50 nm, as determined by scanning electron microscopy (SEM).

[0017] In a seventh aspect, the present disclosure relates to a process of converting an organic compound to a conversion product, which comprises contacting the organic compound with the molecular sieve of the present disclosure or prepared according to the process the present disclosure.

[0018] These and other features and attributes of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows. It will of course be appreciated that features described in relation to one aspect of the present disclosure may be incorporated into other aspects of the present disclosure. In particular, any two or more of the features described in this specification, including in this summary section, can be combined to form combinations of features not specifically described herein.DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 shows the powder XRD pattern of the as-synthesized product of Example2.

[0020] Figure 2 shows the powder XRD pattern of the as-synthesized product of Example3.

[0021] Figure 3 shows SEM images of the as-synthesized product of Example 3.

[0022] Figure 4 shows the powder XRD pattern of the as-synthesized product of Example5.

[0023] Figure 5 shows a SEM image of the as-synthesized product of Example 5.

[0024] Figure 6 shows the powder XRD pattern of the as-synthesized product of Example 10.

[0025] Figure 7 shows a SEM image of the as-synthesized product of Example 10.

[0026] Figure 8 shows the powder XRD pattern of the as-synthesized product of Example 13.

[0027] Figure 9 shows SEM images of the as-synthesized product of Example 13.

[0028] Figure 10 shows SEM images of the as-synthesized product of Example 16.

[0029] Figure 11 shows the powder XRD pattern of the as-synthesized product of Example17.

[0030] Figure 12 shows SEM images of the as-synthesized product of Example 17.

[0031] Figure 13 shows molar ratios and conditions used for the syntheses of Examples 2 to 19.DETAILED DESCRIPTION OF THE INVENTION

[0032] The present disclosure relates to methods of making EMM-73 molecular sieves. EMM-73 molecular sieves may also be designated as EMM-73 zeolites, or EMM-73 materials.

[0033] In a first aspect, the present disclosure relates to a method of making EMM-73 molecular sieve in hydroxide media, comprising the following steps:(a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of hydroxide ions (OH), and optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4- azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquaternary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III:Formula III where R is selected from methyl, ethyl, and n-propyl, R’ is selected from methyl, ethyl and n- propyl, and n is 4 to 10, and wherein, if Y is Si, X is Al, the structure directing agent (Q) is 1,5 -diethyl-5 -azaindolium or 1- propyl-5-methyl-5-azaindolium, and in the absence of seed crystals, an alkali and / or alkaline earth metal element (M) is present in a M / OH molar ratio of more than 0.5;(b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve;(c) recovering at least a portion of the molecular sieve from step (b); and(d) optionally treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

[0034] In a second aspect, the present disclosure relates to a method of making EMM-73 molecular sieve in fluoride media, comprising the following steps:(a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), optionally a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, 5-azaindolium monoquaternary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III:Formula III where R is selected from methyl, ethyl, and n-propyl, in Formula I R’ is selected from methyl, ethyl and n-propyl, in Formula II R’ is methyl or n-propyl, and n is 4, 5, 7, 9 or 10,(b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve;(c) recovering at least a portion of the molecular sieve from step (b); and(d) optionally treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

[0035] In the first and second aspects of the present disclosure, the synthesis mixture comprises at least one source of an oxide of tetravalent element Y such as Si, Ti, and / or Ge, preferably Y comprises Si, and more preferably Y is Si. Suitable sources of tetravalent element Y that can be used to prepare the synthesis mixture depend on the element Y that is selected. In embodiments where Y is silicon, Si sources (e.g., silicon oxide sources) suitable for use in the method include silicates, e.g., tetraalkyl orthosilicates such as tetramethylorthosilicate (TMOS) and tetraethylorthosilicate (TEOS), fumed silica such as Aerosil® (available from Evonik), Cabosperse® (available from Cabot) and Cabosil® (available from DMS), precipitated silica such as Ultrasil® and Sipemat® 340 (available from Evonik), or Hi-Sil®, alkali metal silicates such as potassium silicate and sodium silicate, and aqueous colloidal suspensions of silica, for example, that sold by E.l. du Pont de Nemours under the tradenameLudox® or that sold by Evonik under the tradename Aerodisp®; preferably silicates, fumed silica, precipitated silica, faujasite zeolites, alkali metal silicates, and colloidal silica. In embodiments where Y is germanium, suitable Ge sources include germanium oxide. In embodiments where Y is titanium, suitable Ti sources include titanium dioxide and titanium tetraalkoxides, such as titanium (IV) tetraethoxide and titanium (IV) tetrachloride.

[0036] In the first and second aspects of the present disclosure, the synthesis mixture may comprise or comprises at least one source of an oxide of trivalent element X such as Al, B, Fe and / or Ga, preferably X comprises Al and / or B, e.g., Al, and more preferably X is Al and / or B, e.g., Al. Suitable sources of trivalent element X that can be used to prepare the synthesis mixture depend on the element X that is selected. In embodiments where X is aluminum, Al sources (e.g., aluminum oxide sources) suitable for use in the method include aluminum hydroxide, aluminum salts, especially water-soluble salts, such as aluminum sulfate, aluminum nitrate, alkali metal aluminates such as sodium or potassium aluminate, and aluminum alkoxides such as aluminum isopropoxide, as well as hydrated aluminum oxides, such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other aluminum sources include, but are not limited to, other water-soluble aluminum salts, or aluminum metal, such as aluminum in the form of chips. Especially suitable sources of alumina are aluminum hydroxide and water-soluble salts, such as aluminum sulfate, aluminum nitrate, and alkali metal aluminates such as sodium aluminate and potassium aluminate. In embodiments where X is boron, suitable B sources include boric acid and borate salts such as sodium tetraborate or borax and potassium tetraborate. Sources of boron tend to be more soluble than sources of aluminum in hydroxide-mediated synthesis systems.

[0037] Alternatively or in addition to previously mentioned sources of Y and X, sources containing both Y and X elements can also be used, such as sources of Si and Al. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gels or dried silica alumina powders, silica aluminas, clays, such as kaolin, metakaolin, and zeolites, in particular aluminosilicates such as synthetic faujasite and ultrastable faujasite, for instance Y-Type Zeolite, Ultrastable Y (USY), beta or other large to medium pore molecular sieves or zeolites. Aluminosilicates such as synthetic faujasite and ultrastable faujasite are especially suitable sources of Si and Al.

[0038] In a preferred embodiment of the first aspect of the present disclosure, Y is Si, X is Al and / or B, and the molecular sieve is an aluminosilicate, a borosilicate or an aluminoborosilicate. In a preferred embodiment of the second aspect of the present disclosure,Y is Si, optional X is Al and / or B, and the molecular sieve is a silicate, an aluminosilicate, a borosilicate or an aluminoborosilicate.

[0039] The synthesis mixture of the present disclosure comprises at least one of a source of hydroxide ions (OH) or of fluoride ions (F).

[0040] In the first aspect of the present disclosure (“synthesis in hydroxide media”), the synthesis mixture may have a Y / X molar ratio from 5 to 500, such as from 5 to 100, or higher than 100 to 500, for instance from 8 or 10 or 15 to 50, or from higher than 50 to 100, or from higher than 100 to 250, e.g., 10, 15, 30, 50, 100 or 250.

[0041] In this first aspect, the structure directing agent (Q) may be selected from the group consisting of 4-azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III where R is selected from methyl, ethyl, and n-propyl, R’ is selected from methyl, ethyl and n- propyl, and n is 4 to 10, such as 4 to 8, or 6 to 8, e.g. , 6, 7 or 8. In the cations of Formula I andII, R and R’ may be the same or different, for instance the same. In a first embodiment, the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, where R and R’ are independently selected from methyl, ethyl, and n-propyl, for example R and R’ are the same and are both ethyl. In a second embodiment, the structure directing agent (Q) comprises at least one cation selected from 5- azaindolium monoquatemary cations of Formula II, where R and R’ are independently selected from methyl, ethyl, and n-propyl, for example R is selected from ethyl or n-propyl and R’ is selected from methyl, ethyl and n-propyl. In a third embodiment, the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium diquaternary cations of FormulaIII, where R is selected from methyl, ethyl, and n-propyl, e.g. , methyl or ethyl, and n is 4 to 10, such as 4 to 8, or 6 to 8, e.g. , 6, 7 or 8. Examples of suitable structure directing agents (Q) include cations selected from 1 ,4-diethyl-4-azaindolium, l,5-diethyl-5-azaindolium, l-ethyl-5- propyl-5-azaindolium, l-propyl-5-methyl-5-azaindolium, l-propyl-5-ethyl-5-azaindolium, 5,5'-(octane-l,8-diyl)bis(l-methyl-5-azaindolium), 5,5’-(octane-l,8-diyl)bis(l-ethyl-5- azaindolium), 5,5'-(heptane-l,7-diyl)bis(l-methyl-5-azaindolium), 5,5’-(heptane-l,7- diyl)bis(l-ethyl-5-azaindolium), 5,5'-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium), 5,5'- (hexane-l ,6-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-methyl-5- azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium), 5,5’-(butane-l,4-diyl)bis(l- methyl-5-azaindolium), or 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium), e.g., 1,4-diethyl- 4-azaindolium, l,5-diethyl-5-azaindolium, l-ethyl-5-propyl-5-azaindolium, l-propyl-5-methyl-5-azaindolium, l-propyl-5-ethyl-5-azaindolium, 5,5’-(octane-l,8-diyl)bis(l-methyl-5- azaindolium), 5,5'-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(hexane-l,6-diyl)bis(l- methyl-5-azaindolium), and 5,5'-(hexane-l,6-diyl)bis(l-ethyl-5-azaindolium). The structure directing agent (Q) may be present in any suitable form, for example as a halide, such as a fluoride, a chloride, an iodide or a bromide, as a hydroxide or as a nitrate, for instance in its hydroxide form. The structure directing agent (Q) may be present in the synthesis mixture in a Q / Y molar ratio of from 0.01 to 1.0, such as from 0.05 to 0.8, or 0.1 to 0.7, advantageously 0.05 to 0.5, or 0.1 to 0.4, e.g., 0.05 to 0.3.

[0042] In this first aspect, the synthesis mixture comprises at least one source of hydroxide ions (OH). For example, hydroxide ions can be present as a counter ion of the structure directing agent (Q) or by the use of aluminum hydroxide or sodium aluminate as a source of Al. Suitable sources of hydroxide ions can also be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; such as from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more often sodium hydroxide, potassium hydroxide, rubidium hydroxide, ammonium hydroxide, and mixtures thereof; most often sodium hydroxide and / or rubidium hydroxide, e.g., sodium hydroxide. In this first aspect, the hydroxide ions source may be present in the synthesis mixture in a OH / Y molar ratio of from 0.05 to 1.5, such as from 0.1 to 1.0, for instance from 0.15 to 0.8, or from 0.2 to 0.7 or to 0.6, e.g., 0.2, 0.3, 0.4 or 0.5.

[0043] In this first aspect, the synthesis mixture may optionally comprise one or more sources of alkali or alkaline earth metal cation (M). If present, M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, calcium, magnesium, strontium, barium, and mixtures thereof, preferably sodium, potassium, rubidium, and mixtures thereof, more preferably sodium and / or rubidium, most preferably sodium. The sodium source, when present, may be sodium hydroxide, sodium aluminate, sodium silicate, or sodium salts such as NaCl, NaBr or sodium nitrate. The potassium source, when present, may be potassium hydroxide, potassium aluminate, potassium silicate, a potassium salt such as KC1 or KBr or potassium nitrate. The lithium source, when present, may be lithium hydroxide or lithium salts such as LiCI , LiBr, Lil, lithium nitrate, or lithium sulfate. The rubidium source, when present, may be rubidium hydroxide or rubidium salts such as RbCl, RbBr, Rbl, or rubidium nitrate. The cesium source, when present, may be cesium hydroxide, The calcium source, whenpresent, may be calcium hydroxide. The magnesium source, when present, may be magnesium hydroxide. The strontium source, when present, may be strontium hydroxide. The barium source, when present, may be barium hydroxide. The alkali or alkaline earth metal cation M may also be present in the one or more sources of alumina, such as sodium aluminate or potassium aluminate and / or in the one or more sources of silica, such as potassium silicate and / or sodium silicate. The source of alkali or alkaline earth metal cation (M) is advantageously soluble in water. The synthesis mixture may comprise the alkali or alkaline earth metal cation (M) source in a M / Y molar ratio of from 0 or 0.01 to 1 .0, such as (if present) from 0.05 to 0.7, for instance from 0.08 to 0.5, e.g., 0.1, 0.2 or 0.3. Preferably, the synthesis mixture comprises one or more sources of alkali or alkaline earth metal cation (M). Alternatively, the synthesis mixture may be substantially free from alkali or alkaline earth metal cation (M). In this first aspect, when Y is Si, X is Al, the structure directing agent (Q) is 1 ,5-diethyl-5-azaindolium or l-propyl-5-methyl-5-azaindolium, and in the absence of seed crystals, should an alkali and / or alkaline earth metal element (M) be present, it should be added in a M / OH molar ratio of more than 0.5, such as at least 0.55 or at least 0.6. In such case, the M / OH molar ratio is typically at most 2, such as at most 1.5, for instance at most 1.0 or less than 1.0.

[0044] In this first aspect, the synthesis mixture is preferably substantially free of fluoride ions (F). This means that no source of fluoride ions is added to the synthesis mixture in any substantial amount, e.g., the synthesis mixture has a F / Y molar ratio of less than 0.05, in particular less than 0.01 or even less than 0.005, such as 0. Said fluoride ions (F), if present, may originate from any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture, such as hydrogen fluoride (HF); salts containing one or several fluoride ions, such as metal fluoride, preferably where the metal is an alkali or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium or barium, or a metal such as aluminum (AIF3, AhFe) or tin (SnF2); ammonium fluoride (NH4F); and ammonium bifluoride (NH4HF2). Small amounts of fluoride ions (F) may also be present as impurities, for instance in the optional source of alkali or alkaline earth metal cation (M).

[0045] In this first aspect, the synthesis mixture may optionally contain at least one source of halide ions (W), different from fluoride ions, which may be selected from the group consisting of chloride, bromide or iodide. The source of halide ions (W) may be any compound capable of releasing halide ions in the molecular sieve synthesis mixture. For instance, halide ions can be present as a counter ion of the structure directing agent (Q). Non-limiting examples of sources of halide ions include hydrogen chloride, ammonium chloride, hydrogen bromide,ammonium bromide, hydrogen iodide, and ammonium iodide; salts containing one or several halide ions, such as metal halides, preferably where the metal is an alkali or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium or barium; or tetraalkylammonium halides such as tetramethylammonium halides or tetraethylammonium halides. Small amounts of halide ions (W) may also be present as impurities, for instance in the optional source of alkali or alkaline earth metal cation (M). The halide ions (W) may be present in a W / Y molar ratio of 0 to 0.5, such as 0 to 0.3, for instance 0.1 or 0.2. Alternatively, the synthesis mixture may be substantially free from halide ions (W).

[0046] In this first aspect, the synthesis mixture may comprise water in a H2O / Y molar ratio of from 1 to 100, such as 5 to 80 or 8 to 70, for instance 10 to 50, or 15 to 40, e.g., 10, 20, 30 or 50. Depending on the nature of the components in the base mixture, the amount of solvent (e.g., water from the hydroxide solution, and optionally methanol and ethanol from the hydrolysis of silica sources) of the base mixture may be removed such that a desired solvent to Si molar ratio is achieved for the synthesis mixture. Suitable methods for reducing the solvent content may include evaporation under a static or flowing atmosphere such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. Water may also be added to the resulting mixture to achieve the desired H2O / Y molar ratio when too much water is removed during the solvent removal process. In some examples, water removal is not necessary when the preparation have sufficient H2O / Y molar ratio.

[0047] Suitable synthesis mixture compositions for the first aspect of the present disclosure, in terms of molar ratios, are illustrated in the Table 1 below:Table 1 - Synthesis MixturesMolar ratios Typical range Preferred range More preferred rangeY / X 5 - 500 5 - 100 8 - 50Q / Y 0.01 - 1.0 0.05 - 0.8 0.1 - 0.7OH / Y 0.05 - 1.5 0.1 - 1.0 0.2 - 0.8M / Y 0 - 1.0 0.05 - 0.7 (if present) 0.08 - 0.5 (if present)H2O / Y 1 - 100 8 - 70 10 - 50

[0048] In the second aspect of the present disclosure (“synthesis in fluoride media”), when X is present, the synthesis mixture may have a Y / X molar ratio from 5 to 500, such as 5 to 100,or higher than 100 to 500, for instance from 8 or 10 or 15 to 50, or from higher than 50 to 100, or from higher than 100 to 250, e.g., 15, 30, 50 or 100.

[0049] In this second aspect, the structure directing agent (Q) may be selected from the group consisting of 4-azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III where R is selected from methyl, ethyl and n-propyl, in Formula I R’ is selected from methyl, ethyl and n-propyl, in Formula II R’ is selected from methyl or n-propyl, and n is 4, 5, 7, 9 or 10, e.g., 4, 5 or 7. In the cations of Formula I and II, R and R’ may be the same or different, for instance the same. In a first embodiment, the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, where R and R’ are independently selected from methyl, ethyl, and n-propyl, for example R and R’ are the same and are both ethyl. In a second embodiment, the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium monoquatemary cations of Formula II where R is selected from methyl, ethyl, and n-propyl, and R’ is selected from methyl or n-propyl, for example R is selected from ethyl or n-propyl and R’ is selected from methyl or n-propyl. In a third embodiment, the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium diquatemary cations of Formula III, where R is selected from methyl, ethyl, and n-propyl, e.g., ethyl, and n is 4, 5, 7, 9 or 10, e.g., 4, 5 or 7. Examples of suitable structure directing agents (Q) include cations selected from 1 ,4-diethyl-4-azaindolium, l-ethyl-5-propyl- 5-azaindolium, 5,5'-(heptane-l,7-diyl)bis(l-methyl-5-azaindolium), 5, 5 ’-(heptane- 1,7- diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-methyl-5-azaindolium), 5,5'- (pentane-l,5-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(butane-l,4-diyl)bis(l-methyl-5- azaindolium), or 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium), e.g. , l-ethyl-5-propyl-5- azaindolium, 5,5’-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l- ethyl-5-azaindolium), or 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium). The structure directing agent (Q) may be present in any suitable form, for example as a halide, such as a fluoride, a chloride, an iodide or a bromide, as a hydroxide or as a nitrate, for instance in its hydroxide form. The structure directing agent (Q) may be present in the synthesis mixture in a Q / Y molar ratio of from 0.01 to 1.0, such as from 0.05 or from 0.1 to 1.0, or from 0.2 to 0.8, advantageously from 0.2 or 0.3 to 0.7 or 0.6, e.g., 0.25 to 0.5.

[0050] In this second aspect, the synthesis mixture comprises at least one source of fluoride ions (F). The source of fluoride ions (F) may be any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture. For instance, fluoride ions can be present as acounter ion of the structure directing agent (Q). Non-limiting examples of sources of fluoride ions (F) include hydrogen fluoride (HF); salts containing one or several fluoride ions, such as metal fluoride, preferably where the metal is an alkali or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium or barium, or a metal such as aluminum (AIF3, AhFe) or tin (SnFz): ammonium fluoride (NH4F); and ammonium bifluoride (NH4HF2). Especially convenient sources of fluoride ions are HF, NH4F, and NH4HF2, in particular HF. Small amounts of fluoride ions (F) may also be present as impurities, for instance in the optional source of alkali or alkaline earth metal cation (M). In this second aspect, the fluoride ions (F) may be present in the synthesis mixture in a F / Y molar ratio of from 0.05 to 2.0, for instance 0.1 to 1.5, such as 0.15 or 0.2 or 0.3 to 1.0 or 0.8, e.g., 0.5.

[0051] In this second aspect, the synthesis mixture may optionally comprise at least one source of hydroxide ions (OH). For example, hydroxide ions can be present as a counter ion of the structure directing agent (Q) or by the use of aluminum hydroxide or sodium aluminate as a source of Al. Suitable sources of hydroxide ions can also be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; such as from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof; more often sodium hydroxide, potassium hydroxide, rubidium hydroxide, ammonium hydroxide, and mixtures thereof; most often sodium hydroxide and / or rubidium hydroxide, e.g., sodium hydroxide. The synthesis mixture may comprise the hydroxide ions source in an OH / Y molar ratio of from 0 to 1.5, such as (if present) from 0.05 or 0.1 to 1.0, for instance from 0.15 to 0.8, or from 0.2 to 0.7 or 0.6, e.g., 0.5. Alternatively, the synthesis mixture may be substantially free from a hydroxide source.

[0052] In this second aspect, the synthesis mixture may optionally comprise one or more sources of alkali or alkaline earth metal cation (M). If present, M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, calcium, magnesium, strontium, barium, and mixtures thereof, preferably sodium, potassium, rubidium, and mixtures thereof, more preferably sodium and / or rubidium, most preferably sodium. The sodium source, when present, may be sodium hydroxide, sodium aluminate, sodium silicate, or sodium salts such as NaCl, NaBr or sodium nitrate. The potassium source, when present, may be potassium hydroxide, potassium aluminate, potassium silicate, a potassium salt such as KC1 or KBr or potassium nitrate. The lithium source, when present, may be lithium hydroxide or lithium salts such as LiCl, LiBr, Lil. lithium nitrate, or lithium sulfate, The rubidium source, when present,may be rubidium hydroxide or rubidium sails such as RbCl, RbBr, Rbl, or rubidium nitrate. The cesium source, when present, may be cesium hydroxide. The calcium source, when present, may be calcium hydroxide. The magnesium source, when present, may be magnesium hydroxide. The strontium source, when present, may be strontium hydroxide. The barium source, when present, may be barium hydroxide. The alkali or alkaline earth metal cation (M) may also be present in the one or more sources of alumina, such as sodium aluminate or potassium aluminate and / or in the one or more sources of silica, such as potassium silicate and / or sodium silicate. The source of alkali or alkaline earth metal cation (M) is advantageously soluble in water. The synthesis mixture may comprise the alkali or alkaline earth metal cation (M) source in a M / Y molar ratio of 0 to 1.0, such as (if present) 0.01 to 0.5, for instance 0.01 to 0.2, e.g., 0 or 0.01 to 0.1, advantageously less than 0.1, such as at most 0.05. Preferably, the synthesis mixture may be substantially free from alkali or alkaline earth metal cation (M). This means that no source of alkali or alkaline earth metal cation (M) is added to the synthesis mixture in any substantial amount, e.g., the synthesis mixture has a M / Y molar ratio of less than 0.05, in particular less than 0.01 or even less than 0.005, such as 0.

[0053] In this second aspect, the synthesis mixture may optionally contain at least one source of halide ions (W), different from fluoride ions, which may be selected from the group consisting of chloride, bromide, or iodide. The source of halide ions (W) may be any compound capable of releasing halide ions in the molecular sieve synthesis mixture. For instance, halide ions can be present as a counter ion of the structure directing agent (Q). Nonlimiting examples of sources of halide ions include hydrogen chloride, ammonium chloride, hydrogen bromide, ammonium bromide, hydrogen iodide, and ammonium iodide; salts containing one or several halide ions, such as metal halides, preferably where the metal is an alkali or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium, or barium; or tetraalkylammonium halides such as tetramethylammonium halides or tetraethylammonium halides. Small amounts of halide ions (W) may also be present as impurities, for instance in the optional source of alkali or alkaline earth metal cation (M). The halide ions (W) may be present in a W / Y molar ratio of 0 to 0.5, such as 0 to 0.3, for instance 0.1 or less than 0.1 or even 0. Alternatively, the synthesis mixture may be substantially free from halide ions (W).

[0054] In this second aspect, the synthesis mixture typically comprises water in a H2O / Y molar ratio of from 1 to 50, such as 2 to 40 or 3 to 30, for instance 3 to 15, e.g. , 4 or 5.

[0055] Depending on the nature of the components in the base mixture, the amount of solvent (e.g., water from the hydroxide solution, and optionally methanol and ethanol from the hydrolysis of silica sources) of the base mixture may be removed such that a desired solvent to Si molar ratio is achieved for the synthesis mixture. Suitable methods for reducing the solvent content may include evaporation under a static or flowing atmosphere such as ambient air, dry nitrogen, dry air, or by spray drying or freeze drying. Water may also be added to the resulting mixture to achieve the desired H2O / Y molar ratio when too much water is removed during the solvent removal process. In some examples, water removal is not necessary when the preparation have sufficient H2O / Y molar ratio.

[0056] Suitable synthesis mixture compositions for the second aspect of the present disclosure, in terms of molar ratios, are illustrated in the Table 2 below:Table 2 - Synthesis Mixtures in Fluoride MediaMolar ratios Typical range Preferred range More preferred rangeY / X 5 - 500 5 - 100 8 - 50Q / Y 0.01 - 1.0 0.05 - 1.0 0.2 - 0.8F / Y 0.05 - 2.0 0.1 - 1.5 0.2 - 1.0OH / Y 0 - 1.5 0.1 - 1.0 (if present) 0.2 - 0.8 (if present)M / Y 0 - 1.0 0.01 - 0.5 (if present) 0.01 - 0.2 (if present)H2O / Y 1 - 50 2 - 30 3 - 15

[0057] The synthesis of the present disclosure, whether according to the first or second aspect, may be performed with or without added nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds should be of SFS framework type, for instance EMM-73 molecular sieve obtained from a previous synthesis. Such seeds may suitably present in an amount from about 0.01 ppm by weight to about 10,000 ppm by weight, based on the synthesis mixture, such as from about 100 ppm by weight to about 5,000 ppm by weight of the synthesis mixture.

[0058] Carbon in the form of CH2 may be present in the various sources of components used to prepare the molecular sieve of the present disclosure, e.g., silica source or alumina source, and incorporated into the resulting molecular sieve framework as bridging atoms.Nitrogen atoms may be incorporated into the framework of the molecular sieve material as bridging atoms after the SDA has been removed.

[0059] In one or more aspects, the synthesis mixture after solvent adjustment (e.g., where the desired water to silica ratio is achieved) may be mixed by a mechanical process such as stirring or high shear blending to assure suitable homogenization of the base mixture, for example, using dual asymmetric centrifugal mixing (e.g., a FlackTek speedmixer) with a mixing speed of 1000 to 3000 rpm (e.g. , 2000 rpm).

[0060] The synthesis mixture is then subject to crystallization conditions suitable for the molecular sieve material to form. Crystallization of the molecular sieve may be carried out under static or stirred conditions in a suitable reactor vessel, such as for example Teflon® lined or stainless-steel autoclaves placed in a convection oven maintained at an appropriate temperature.

[0061] The crystallization in step (b) of the method is typically carried out at a temperature of 100°C to 200°C, such as 120°C to 180°C, preferably 150°C to 170°C, e.g. , 160°C, for a time sufficient for crystallization to occur at the temperature used. For instance, at higher temperatures, the crystallization time may be reduced. For instance, the crystallization conditions in step (b) of the method may include heating for a period of from 1 to 100 days, such as from 1 to 50 days, for example from 1 to 30 days, e.g., at least 1 or at least 5 days up to 30 or 20 days. In a particularly preferred embodiment, in hydroxide media, the crystallization conditions in step (b) may include heating for a particularly short period of time, such as from 1 to less than 20 days, in particular from 2 to less than 14 days, for example from 3 to 12 days, e.g. , for about 5, 7, 8 or 12 days. The crystallization time can be established by methods known in the art such as by sampling the synthesis mixture at various times and determining the yield and X-ray crystallinity of precipitated solid. Unless indicated otherwise herein, the temperature measured is the temperature of the surrounding environment of the material being heated, for example the temperature of the atmosphere in which the material is heated.

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

[0063] The molecular sieve of the present disclosure, when employed either as an adsorbent or as a catalyst in an organic compound conversion process may be dehydrated (e.g., dried) at least partially. This can be done by heating to a temperature in the range of 80°C to 500°C, such as 90°C to 370°C in an atmosphere such as air, nitrogen, etc., and at atmospheric,sub-atmospheric or super-atmospheric pressures for between 30 minutes and 48 hours. Dehydration may also be performed at room temperature merely by placing the molecular sieve in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.

[0064] As a result of the crystallization process, the recovered product contains within its pores at least a portion of the structure directing agent used in the synthesis. The as-synthesized molecular sieve recovered from step (c) may thus be subjected to thermal treatment or other treatment to remove part or all of the SDA incorporated into its pores during the synthesis. Thermal treatment (e.g., calcination) of the as-synthesized molecular sieve typically exposes the materials to high temperatures sufficient to remove part or all of the SDA, in an atmosphere selected from air, nitrogen, ozone or a mixture thereof in a furnace. While sub- atmospheric pressure may be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment may be performed at a temperature up to 925°C e.g., 300°C to 700°C or 400 to 600°C. The temperature measured is the temperature of the surrounding environment of the sample. The thermal treatment e.g., calcination) may be carried out in a box furnace in dry air, which has been exposed to a drying tube containing drying agents that remove water from the air. The material is usually calcined for at least 1 minute and generally no longer than 1 or at most a few days. The heating may first be carried out under a nitrogen atmosphere and then the atmosphere may be switched to air and / or ozone.

[0065] The molecular sieve material may also be subjected to an ion-exchange treatment, for example, with aqueous ammonium salts, such as ammonium nitrates, ammonium chlorides, and ammonium acetates, in order to remove remaining alkali metal cations and / or alkaline earth metal cations, if present in the synthesis mixture, and to replace them with protons thereby producing the acid form of the molecular sieve. To the extent desired, the original cations of the as-synthesized material, such as alkali metal cations, can be replaced by ion exchange with other cations. Preferred replacing cations can include hydrogen ions, hydrogen precursor, e.g., ammonium ions and mixtures thereof. The ion exchange step may take place after the as-made molecular sieve is dried. The ion-exchange step may take place either before or after a calcination step.

[0066] The molecular sieve material may also be subjected to other treatments such as steaming and / or washing with solvent. Such treatments are well-known to the skilled person and are carried out in order to modify the properties of the molecular sieve as desired.

[0067] The methods of the present disclosure are especially advantageous in that they allow the preparation of EMM-73 molecular sieves with a wide variety of Y / X molar ratios e.g., ofabout 5 to infinity, in particular higher than 100) in hydroxide or fluoride media, including the direct preparation of aluminum-containing and / or boron-containing EMM-73 molecular sieves having a wide variety of Y / Al molar ratios (e.g., of about 5 to infinity, in particular higher than 100). The methods of the present disclosure are also advantageous in that they allow the preparation of EMM-73 molecular sieve with a controlled morphology, in particular the preparation of nanosized crystals (for instance having a (average) maximal particle size as small as less than 100 nm) which are advantageous for catalysis. The methods of the present disclosure are also especially advantageous in that they use simple and scalable organic structure direct agents (Q), much more robust than the benzimidazolium structure directing agents of the prior art. In particular, the azaindolium SDAs of the present invention are cheaper and more easily scalable than the benzimidazolium SDAs of the prior art.

[0068] In a third aspect, the present disclosure relates to an EMM-73 molecular sieve, in particular to an EMM-73 molecular sieve prepared according to the first or second aspect of the present disclosure, having at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III as defined above within its pore structure. Said molecular sieve may be represented by the molecular formula of Formula IV:(q)Q : (m)X2O3: YO2(Formula IV), wherein 0<q<1.0, 0<m<0.1, X is a trivalent element, Y is a tetravalent element, and Q comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, 5-azaindolium monoquaternary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III as defined above. Y may comprise one or more of Si, Ti and Ge. For example, Y may comprise or be Si. X may comprise one or more of Al, B, Fe and Ga. In particular, X may comprise or be Al and / or B, for example X may comprise or be Al. In embodiments where Y is Si, m is higher than 0, and X is Al and / or B, the molecular sieve is an aluminosilicate, a borosilicate or an aluminoborosilicate. In embodiments where Y is Si and m is 0, the molecular sieve is a silicate. The oxygen atoms in Formula IV may be replaced by carbon atoms (e.g. , in the form of CH2), which can come from sources of the components used to prepare the as-made molecular sieve. The oxygen atoms in Formula IV can also be replaced by nitrogen atoms, e.g., after the SDA has been removed. Formula IV can represent the framework of a typical EMM-73 molecular sieve material having structure directing agent (Q) within its pore structure and is not meant to be the sole representation of such material. Themolecular sieve may contain impurities which are not accounted for in Formula IV. Further, Formula IV does not include the protons and charge compensating ions that may be present in the molecular sieve material.

[0069] The variable m represents the molar ratio relationship of X2O3 to Y O2 in Formula IV. For example, when m is 0.01, the molar ratio of YO2 to X2O3 is 100 and the Y / X molar ratio is 50. m may vary from 0 to 0. 1, such as from 0.001 to less than 0.005, or from 0.005 to 0.1, for instance from 0.002 to less than 0.005, or from 0.005 to less than 0.01, or from 0.01 to 0.06. The molar ratio of Y to X may be from 5 to 500, such as from 5 to 100, or higher than 100 to 500, for instance from 8 to 50, or from higher than 50 to 100, or from higher than 100 to 250.

[0070] The variable q represents the molar relationship of Q to YO2 in Formula IV. For example, when q is 0.1 , the Q / Y molar ratio is 0. 1 . The molar ratio of Q to YO2 may be from 0.01 to 1.0, such as from 0.05 or from 0.1 to 1.0 or to 0.8, or from 0.1 or from 0.2 to 0.7, e.g., 0.05 to 0.5.

[0071] In a fourth aspect, the present disclosure relates to an EMM-73 molecular sieve obtainable by (or obtained by) the method of the first or second aspect of the present disclosure. Said EMM-73 molecular sieve may have, in its as-synthesized form (e.g., where the SDA has not been removed) and / or calcined form e.g. , where at least part of the SDA has been removed via thermal treatment or other treatment), X-ray diffraction (XRD) patterns similar to those of EMM-73 molecular sieve as disclosed in WO2023 / 168174, incorporated herein by reference. More particularly, said EMM-73 molecular sieve may have, in its as-synthesized and calcined forms, XRD patterns including the peaks of respectively Tables 1 (or 1A) and 2 (or 2 A) of WO2023 / 168174.

[0072] The EMM-73 molecular sieve of the present disclosure, in particular the EMM-73 molecular sieve of the third or fourth aspect of the present disclosure, may advantageously have a high Y / X molar ratio, such as a Y / X molar ratio of more than 100, for instance higher than 100 to 500, e.g., higher than 100 to 250, as determined by ICP elemental analysis. In a fifth aspect, the present disclosure therefore relates to an EMM-73 molecular sieve characterized by a Y / X molar ratio of more than 100, for instance higher than 100 to 500, e.g, higher than 100 to 250, as determined by ICP.

[0073] The EMM-73 molecular sieve of the present disclosure, in particular the EMM-73 molecular sieve of the third, fourth or fifth aspect of the present disclosure, may advantageously have a small particle size (or crystal size or crystallite size). More particularly, at least a portionof the EMM-73 molecular sieve of the present disclosure, whether in as-synthesized or calcined form, may have a maximal particle size, defined as the maximal dimension of the particle, of less than 2 microns, in particular of less than 1 micron, more particularly of less than 0.8 micron, most particularly of less than 0.5 micron, or even less than 100 nm or less than 50 nm. For instance, the maximal particle size may be from 50 or 75 to less than 500 nm, e.g., from 100 to 200 nm, or from 200 to 300 nm or from 300 to 500 nm. In other embodiments, the maximal particle size may even be as low as 10 to less than 50 nm, or from 50 to less than 100. By “at least a portion” is meant at least about 50% of the molecular sieve crystals, such as at least 60%, at least 75%, or at least 85%. The maximal dimension of the particles as well as the percentage (as vol%) of particles having said maximal dimension can be determined by image analysis, for example, of scanning electron microscopy (SEM) micrographs, e.g. , using ImageJ software. In a further or another embodiment, the molecular sieve of the present disclosure (whether in as-synthesized or calcined form) may have an average maximal particle size of less than 2 microns, in particular of less than 1 micron, more particularly of less than 0.8 micron, most particularly of less than 0.5 micron, or even less than 100 nm or less than 50 nm. For instance, the average maximal particle size may be from 50 or 75 to less than 500 nm, e.g., from 100 to 200 nm, or from 200 to 300 nm or from 300 to 500 nm. In other embodiments, the average maximal particle size may even be as low as 10 to less than 50 nm, or from 50 to less than 100. The average maximal particle size can be defined as the average (or arithmetic mean) of the maximal dimension of particles measured from randomly selected SEM micrographs from which were selected at least one hundred particles. In a sixth aspect, the present disclosure therefore relates to an EMM-73 molecular sieve, advantageously an aluminosilicate or an aluminoborosilicate EMM-73 molecular sieve, characterized by a maximal particle size and / or an average maximal particle size of less than 100 nm, such as less than 75 nm or even of less than 50 nm, e.g., from 10 to less than 100 nm, or from 10 to less than 75 nm, or from 10 to less than 50 nm, as determined by scanning electron microscopy (SEM).

[0074] In further embodiments of the third, fourth, fifth or sixth aspects of the present disclosure, at least a portion of the EMM-73 molecular sieve crystals, whether in as-synthesized or calcined form, may have a plate-like or a rectangular-like morphology. By “at least a portion” of the molecular sieve crystals may have a plate-like or a rectangular-like morphology is meant at least about 50% of the molecular sieve crystals can have a plate-like or a rectangular-like morphology, such as at least 60%, at least 75%, or at least 85%.

[0075] By “plate-like morphology” is meant crystals that are substantially in the form ofplatelets, for instance of discs or rectangular plates, having first and second major dimensions that can be referred to as the length (1) and the breadth (b) of the platelet (z.<?., the longest dimension of the biggest face of the platelet and the dimension of said biggest face measured at the middle and perpendicular to said longest dimension) and a minor third dimension that can be referred to as the thickness (t) of the platelet ( / .<?., smallest dimension measured at the middle of the longest dimension, perpendicular to said biggest face). The morphology as well as the percentage (as vol%) of crystals having said morphology can be determined by image analysis, for example, of scanning electron microscopy (SEM) micrographs, e.g. , using Imaged software. The molecular sieve crystals having a plate-like morphology according to the present disclosure may for instance have a length to breadth ratio (1 / b) of from 1 to less than 10, such as from 1 to 8, or from 1 to 6, e.g., from 1 or 2 to 3, and a length to thickness ratio (1 / t) of at least 10, such as from 10 to 50, or from 10 to 20. The breadth to thickness ratio (b / t) may vary accordingly. In more specific embodiments, the molecular sieve crystals may have a plate-like morphology with length (1) corresponding to a maximal particle size (or an average length (1) corresponding to an average maximal particle size) as defined above.

[0076] By “rectangular-like morphology” is meant crystals that are substantially in the form of rectangular parallelepipeds (or rectangular prism or rectangular cuboids), i.e., parallelepiped whose all six faces possess a substantially rectangular (or square) shape, in particular with one long dimension and two short dimensions where the one long dimension can be referred to as the length (I) of the rectangular parallelepiped (i.e., the longest side of the biggest face) and the two short dimensions can be referred to as the width (w) and height (h) of the rectangular parallelepiped i.e., each of the longest dimensions of the particle, perpendicular to its length (1)). The morphology as well as the percentage (as vol%) of crystals having said morphology can be determined by image analysis, for example, of scanning electron microscopy (SEM) micrographs, e.g., using ImageJ software. The molecular sieve crystals having a rectangular- like morphology according to the present disclosure may typically have a length to width ratio (1 / w) of from 1 to less than 10, such as 1 to 6, e.g. , 2 to 3 and a length to height ratio (1 / h) of from 1 to less than 10, such as from 1 to 8, or from 1 to 6, e.g., 1 or 2 to 3. The width to height ratio (w / h) may vary accordingly, such as from 1 to 3, e.g. , 1 to 2. In a specific embodiment, the molecular sieve crystals may have a rectangular-like morphology with a length (1) corresponding to a maximal particle size (or an average length (1) corresponding to an average maximal particle size) as defined above.

[0077] The EMM-73 molecular sieve of the present disclosure, in its as-made form, mayoptionally be represented by the molecular formula of Formula IV as defined above. Said EMM-73 molecular sieve, in its calcined form (e.g., where at least part of the SDA has been removed by thermal treatment or other treatment), may optionally be represented by the molecular formula of Formula V:(m)X2O3: YO2(Formula V), wherein 0<m<0.1 , X is a trivalent element as defined for Formula IV and Y is a tetravalent element as defined for Formula IV. The oxygen atoms in Formula V may be replaced by carbon atoms (e.g., in the form of CH2), which can come from sources of the components used to prepare the as-made molecular sieve. The oxygen atoms in Formula V can also be replaced by nitrogen atoms, e.g. , after the SDA has been removed. Formula V can represent the framework of a typical molecular sieve as defined in the present disclosure, in its calcined form, and is not meant to be the sole representation of said molecular sieve. Said molecular sieve, in its calcined form, may contain SDA and / or impurities after appropriate treatments to remove the SDA and impurities, which are not accounted for in Formula V. Further, Formula V does not include the protons and charge compensating ions that may be present in the calcined molecular sieve. The variable m represents the molar ratio relationship of X2O3to YO2in Formula V. The values for variable m in Formula V are the same as those described herein for Formula IV.

[0078] The EMM-73 molecular sieve of the present disclosure, in particular the EMM-73 molecular sieve prepared according to the first or second aspect of the present disclosure, or of any other aspect of the present disclosure, where part or all of the SDA has been removed, may be used as an adsorbent or as a catalyst or support for catalyst in a wide variety of hydrocarbon conversions, e.g. , conversion of organic compounds to a converted product. In a seventh aspect, the present disclosure therefore relates to a process of converting an organic compound to a conversion product, which comprises contacting the organic compound with the molecular sieve of the present disclosure or prepared according to the process the present disclosure.

[0079] The molecular sieve of the present disclosure (where part or all of the SDA is removed) may be used as an adsorbent, such as for separating at least one component from a mixture of components in the vapor or liquid phase having differential sorption characteristics with respect to the material. Therefore, at least one component can be partially or substantially totally separated from a mixture of components having differential sorption characteristics with respect to the molecular sieve by contacting the mixture with said molecular sieve to selectively sorb the one component. For instance, in a process for selectively separating one or moredesired components of a feedstock from remaining components of the feedstock, the feedstock may be contacted with a sorbent that comprises the molecular sieve of the present disclosure at effective sorption conditions, thereby forming a sorbed product and an effluent product. One or more of the desired components are recovered from either the sorbed product or the effluent product.

[0080] The molecular sieve of the present disclosure (where part or all of the SDA is removed) may also be used as a catalyst to catalyze a wide variety of organic compound conversion processes. Examples of chemical conversion processes, which are effectively catalyzed by the molecular sieve described herein, either alone or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity. Examples of organic conversion processes, which may be catalyzed by the molecular sieve described herein, either alone or in combination with one or more other catalytically active substances, including other crystalline catalysts, include cracking, hydrocracking, isomerization, polymerisation, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, adsorption, alkylation, transalkylation, dealkylation, hydrodecylization, disproportionation, oligomerization, dehydrocyclization, conversion of methanol to olefins, deNOx applications, and combinations thereof. The conversion of hydrocarbon feeds can take place in any convenient mode, for example in fluidized bed, moving bed, or fixed bed reactors depending on the types of process desired.

[0081] The molecular sieve of the present disclosure may be formulated into product compositions by combination with other materials, such as binders and / or matrix materials that provide additional hardness to the finished product. These other materials can be inert or catalytically active materials.

[0082] For instance, it may be desirable to incorporate the molecular sieve of the present disclosure with another material that is resistant to the temperatures and other conditions employed during use. Such materials include synthetic or naturally occurring zeolites or molecular sieve as well as inorganic materials such as clays, silica and / or metal oxides such as alumina and mixtures thereof. The metal oxides may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a resistant material in conjunction with the molecular sieve of the present disclosure, i.e., combined therewith or present during synthesis of the as-made molecular sieve, which crystal is active, tends to change the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive resistant materials suitably serve as diluents to control theamount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the product under commercial operating conditions. Said inactive resistant materials, i.e. , clays, oxides, etc., function as binders for the catalyst. A catalyst having good crush strength can be beneficial because in commercial use, it is desirable to prevent the catalyst from breaking down into powder-like materials.

[0083] Naturally occurring clays which may be used include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or after being subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the molecular sieve of the present disclosure also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallium oxide, zinc oxide and mixtures thereof.

[0084] In addition to the foregoing materials, the molecular sieve of the present disclosure may be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica- zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia- zirconia.

[0085] These binder materials are resistant to the temperatures and other conditions, e.g., mechanical attrition, which occur in various hydrocarbon separation processes. Thus the molecular sieve of the present disclosure may be used in the form of an extrudate with a binder. They are typically bound by forming a pill, sphere, or extrudate. The extrudate is usually formed by extruding the molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudate. Further treatments such as steaming, and / or ion exchange may be carried out as required. The molecular sieve may optionally be bound with a binder having a surface area of at least 100 m2 / g, for instance at least 200 m2 / g, optionally at least 300 m2 / g.

[0086] The relative proportions of molecular sieve and inorganic oxide matrix may vary widely, with the molecular sieve content ranging from about 1 to about 100 percent by weight and more usually, particularly when the composite is prepared in the form of extrudates, in therange of about 2 to about 95, optionally from about 20 to about 90 weight percent of the composite.

[0087] The molecular sieve of the present disclosure may also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such hydrogenating components may be incorporated in the composition by way of one or more of the following processes: cocrystallization; exchanged into the composition to the extent a Group IIIA element, e.g., aluminum, is in the structure; or intimately physically admixed therewith. Such components can also be impregnated in or onto the molecular sieve for example, by treating the molecular sieve with a hydrogenating metal-containing ion. For instance, in the case of platinum, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing a platinum amine complex. Combinations of metals and methods for their introduction can also be used.

[0088] It will be understood by a person skilled in the art that the molecular sieve of the present disclosure may contain impurities, such as amorphous materials, unit cells having different topologies (e.g., quartz, zeolites or molecular sieves of different framework type, that may or may not impact the performance of the resulting catalyst), and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). Typical examples of zeolites or molecular sieves of different framework type co-existing with the molecular sieve of the present disclosure are, e.g., zeolites or molecular sieves of MOR, MFI, MEL, MTW, TON or BOG framework type, such as mordenite, ZSM-5, ZSM-11, ZSM-12, ZSM-22 or EMM-76. The molecular sieve of the present disclosure is preferably substantially free of impurities. The term “substantially free of impurities” (or in the alternative “substantially pure”) used herein means the molecular sieve material contains a minor proportion (less than 50 wt%), preferably less than 20 wt %, more preferably less than 10 wt%, even more preferably less than 5 wt% and most preferably less than 1 wt% (e.g., less than 0.5 wt% or 0.1 wt%), of such impurities (or “non-EMM-73” material), which weight percent (wt%) values are based on the combined weight of impurities and pure molecular sieve. The amount of impurities can be appropriately determined by powder XRD, rotating electron diffraction, and / or SEM / TEM (e.g., different crystal morphologies).

[0089] The molecular sieve described herein is substantially crystalline. As used herein, the term “crystalline” refers to a crystalline solid form of a material, including, but not limited to, a single-component or multiple-component crystal form, e.g., including solvates, hydrates,and a co-crystal. Crystalline can mean having a regularly repeating and / or ordered arrangement of molecules, and possessing a distinguishable crystal lattice. For example, the molecular sieve can have different water or solvent content. The different crystalline lattices can be identified by solid state characterization methods such as by XRD (e.g., powder XRD). Other characterization methods known to a person of ordinary skill in the relevant art can further help identify the crystalline form as well as help determine stability and solvent / water content. As used herein, the term “substantially crystalline” means a majority (greater than 50 wt%) of the weight of a sample of a material described is crystalline and the remainder of the sample is a non-crystalline form. In one or more aspects, a substantially crystalline sample has at least 95% crystallinity (e.g., 5% of the non-crystalline form), at least 96% crystallinity (e.g., 4% of the non-crystalline form), at least 97% crystallinity (e.g., 3% of the non-crystalline form), at least 98% crystallinity (e.g., about 2% of the non-crystalline form), at least 99% crystallinity (e.g., 1% of the non-crystalline form), and 100% crystallinity (e.g., 0% of the non-crystalline form).

[0090] Aspects of the disclosure are described in greater detail by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the disclosure in any manner. Those of skill in the relevant art will readily recognize a variety of parameters can be changed or modified to yield essentially the same results.EXAMPLES

[0091] The present invention is further illustrated below without limiting the scope thereto.

[0092] In these examples, the X-ray diffraction (XRD) patterns of the as -synthesized and calcined materials were recorded on a Broker D8 Endeavor Automated X-ray Diffractometer in continuous mode using a Cu Ka radiation, Bragg-Bentano geometry with Vantec 500 detector, in the 20 range of 4 to 40 degrees. The interplanar spacings, d-spacings, were calculated in Angstrom units, and the relative intensities of the lines, / Tois the ratio of the peak intensity to that of the intensity of the strongest line, above background. The intensities are uncorrected for Lorentz and polarization effects. The location of the diffraction peaks in 2- theta, and the relative peak area intensities of the lines, I / I(o), where Io is the intensity of the strongest line, above background, were determined with the MDI Jade peak search algorithm. It should be understood that diffraction data listed as single lines may consist of multiple overlapping lines which under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and / or a change in crystal symmetry, without a change in the framework connectivity. These minor effects, including changes in relativeintensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, crystal size and shape, preferred orientation and thermal and / or hydrothermal history.

[0093] The scanning electron microscopy (SEM) images of the as-synthesized materials were obtained on a Hitachi 4800 Scanning Electron Microscope. SEM images were used to aid assessment of product purity. The presence of obviously different crystal morphologies in a SEM image can be an indication of impurities in the form of other crystalline materials. Such an approximate analysis can be especially useful in identifying the presence of formation of relatively minor amounts of crystalline impurities which may not be identifiable on productXRD patterns.

[0094] The molar ratios and conditions used for the syntheses of Examples 2 to 19, as well as the resulting products, are detailed below and summarized in Figure 13. In Figure 13, it is noted that SDA 1 corresponds to l,5-diethyl-5-azaindolium cation; SDA2 corresponds to 1- ethyl-5-propyl-5-azaindolium cation; SDA3 corresponds to l-propyl-5-ethyl-5-azaindolium cation; SDA4 corresponds to 1 ,4-diethyl-4-azaindolium cation; SDA5 corresponds to 5,5'- (hexane-l ,6-diyl)bis(l-methyl-5-azaindolium) cation; SDA6 corresponds to 5,5'-(hexane-l ,6- diyl)bis(l-ethyl-5-azaindolium) cation; SDA7 corresponds to 5,5'-(pentane-l,5-diyl)bis(l- ethyl-5-azaindolium) cation; SDA8 corresponds to 5,5’-(butane-l,4-diyl)bis(l-ethyl-5- azaindolium) cation; SDA9 corresponds to 5,5’-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium); and SDA10 corresponds to 5,5’-(octane-l,8-diyl)bis(l-ethyl-5-azaindolium).Synthesis of 1,5 -diethyl-5 -azaindolium cation (SDA1)

[0095] 25 g (222 mmol) of 5-azaindole (1 H-pyrrolo[3,2-c] pyridine), 76 g (487 mmol) of iodoethane, and 13.1 g (232 mmol) of potassium hydroxide in 400 mL of acetonitrile were heated to 80°C for 6 hours. The acetonitrile was removed viarotovap and the residue dissolved in 250 mL of chloroform. The potassium salts were removed by filtration and the chloroform removed via rotovap. ' H-NMR showed that the brown solid was l,5-diethyl-5-azaindolium( 1 ,5-diethyl- 1 / / -pyrrolo| 3,2-< |pyridin-5-ium) iodide.

[0096] The iodide salt was ion-exchanged with ion-exchange resin Amberlite® IRN78 OH hydroxide form, with a iodide : resin : water weight ratio of 1 : 3.5: 5, to its hydroxide form.The exchange was performed at room temperature overnight.Synthesis of l-ethyl-5-propyl-5-azaindolium cation (SDA2)

[0097] Synthesis of l-ethyl-5-propyl-5-azaindolium hydroxide was conducted in a similar way to the synthesis of 5-ethyl-l-propyl-5-azaindolium hydroxide of Example 1C, except thatpropyl iodide was replaced with ethyl iodide in the first step, and iodoethane was replaced with iodopropane in the second step.Example 1C: Synthesis of 5-ethyl-l-propyl-5-azaindolium cation (SDA3)

[0098] A solution of 29.7 g potassium hydroxide (85%wt), 50 g of 5-azaindole (1H- pyrrolo[3,2-c] pyridine), and 550 mL of acetonitrile was mixed and stirred for a few hours. Then, 63 g propyl iodide was added dropwise, and the reaction was stirred for 16 hours at room temperature. The solids were filtered and the acetonitrile rotovapped off. The residue was dissolved in 500 mL of ethyl acetate and the organics washed 3 times with 250 mL of water. The organics were dried over magnesium sulfate and removed via rotovap to give l-propyl-5- azaindole ( 1 -propyl- 1 H-pyrrolo [3 ,2-c ]pyridine) .

[0099] 25 g of l-propyl-5-azaindole were dissolved in 200 mL of acetonitrile, then 36 g of iodoethane were added and the mixture was gently refluxed for 16 hours. The acetonitrile was removed via rotovap to obtain 5-ethyl-l-propyL5-azaindolium iodide (5-ethyl-l-propyL177- pyrrolo[3 ,2-c]pyridin-5 -ium iodide) .

[0100] The iodide salt was ion-exchanged with ion-exchange resin Amberlite® IRN78 OH hydroxide form, with a iodide : resin : water weight ratio of 1 : 4: 5, to its hydroxide form. The exchange was performed at room temperature overnight.Example ID: Synthesis of 1 ,4-diethyl-4-azaindolium cation (SDA4)

[0101] Synthesis of l,4-diethyl-4-azaindolium hydroxide was conducted in a similar way to the synthesis of l,5-diethyl-5-azaindolium hydroxide of Example 1A, except that 4- azaindole was used as the organic reagent rather than 5-azaindole.Example IE: Synthesis of 5,5’-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium) cation (SDA5)

[0102] A solution of 29.7 g potassium hydroxide (85%wt), 50 g of 5-azaindole (1H- pyrrolo[3,2-c] pyridine), and 550 mL of acetonitrile was mixed and stirred for a few hours. Then, 63 g methyl iodide was added drop wise, and the reaction was stirred for 16 hours at room temperature. The solids were filtered and the acetonitrile rotovapped off. The residue was dissolved in 500 mL of ethyl acetate and the organics washed 3 times with 250 mL of water. The organics were dried over magnesium sulfate and removed via rotovap to give l-methyl-5- azaindole ( 1 -methyl- 1 H-pyrrolo[3,2-c]pyridine).

[0103] 17.2 g of l-methyl-5-azaindole were dissolved in 200 mL of acetonitrile, then 15.9 g of 1,6-dibromohexane were added and the mixture was gently refluxed for 16 hours. The acetonitrile was removed via rotovap and the residue was washed with 500 mL of ethyl acetate two times by decanting the organics. The residue was rotovapped further to remove any ethylacetate to obtain 5,5’-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium) dibromide (5,5’-(hexane-1 , 6 -diy l)bis ( 1 -methyl- 1 H-pyrrolo[3 ,2-c]pyridin-5 -ium dibromide) .

[0104] The bromide salt was ion-exchanged with ion-exchange resin Amberlite® IRN78OH hydroxide form, with a bromide : resin : water weight ratio of 1 : 4: 5, to its hydroxide form. The exchange was performed at room temperature overnight.Synthesis of 5,5 (hexane- l,6-diyl)bis(l-ethyl-5-azaindolium) cation (SDA6)

[0105] Synthesis of 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5-azaindolium) hydroxide was conducted in a similar way to the synthesis of 5,5’-(hexane-l,6-diyl)bis(l-methyl-5- azaindolium) hydroxide of Example IE, except that methyl iodide was replaced by ethyl iodide.Synthesis of 5,5 (pentane-l,5-diyl)bis(l-ethyl-5-azaindolium) cation (SDA7)

[0106] Synthesis of 5,5’-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium) hydroxide was conducted in a similar way to the synthesis of 5,5’-(hexane-l ,6-diyl)bis(l -ethyl-5- azaindolium) hydroxide of Example IF, except that 1 ,6-dibromohexane was replaced by 1,5- dibromopentane.Synthesis of 5,5 (butane- l,4-diyl)bis(l-ethyl-5-azaindolium) cation (SDA8)

[0107] Synthesis of 5,5’-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium) hydroxide was conducted in a similar way to the synthesis of 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5- azaindolium) hydroxide of Example IF, except that 1 ,6-dibromohexane was replaced by 1,4- dibromobutane.Synthesis of 5,5 (heptane-l,7-diyl)bis(l-ethyl-5-azaindolium) cation (SDA9)

[0108] Synthesis of 5,5’-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium) hydroxide was conducted in a similar way to the synthesis of 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5- azaindolium) hydroxide of Example IF, except that 1 ,6-dibromohexane was replaced by 1,7- dibromoheptane.Synthesis of 5,5 (octane-1, 8-diyl)bis(l-methyl-5-azaindolium) cation (SDA10)

[0109] Synthesis of 5,5’-(octane-l,8-diyl)bis(l-methyl-5-azaindolium) hydroxide was conducted in a similar way to the synthesis of 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5- azaindolium) hydroxide of Example IF, except that 1 ,6-dibromohexane was replaced by 1,8- dibromooctane.Synthesis of EMM-73 in hydroxide media, SDA1 Si / Al 15

[0110] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 4.12 g of l,5-diethyl-5-azaindolium cation (Q) as structure directing agent (hydroxide form, 7.2 wt% solution), 1.23 g of NaOH solution (10 wt%), 0.55 g of deionized water and 0.73 g ofUltrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (available from Zeolyst as CBV720) to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.033 AI2O3 : 0.15 QOH : 0.3 NaOH

[0111] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 5 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0112] Figure 1 shows the powder XRD pattern of the as-synthesized product. XRD analysis showed the material to be EMM-73 molecular sieve with a small amount of MOR impurities.Synthesis of EMM-73 in hydroxide media, SDA1 Si / Al 15

[0113] This example was conducted in similar conditions as Example 2 except for a higher amount of water. More particularly, in a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 2.47 g of l,5-diethyl-5-azaindolium cation (Q) as structure directing agent (hydroxide form, 7.2 wt% solution), 0.74 g of NaOH solution (10 wt%), 2.55 g of deionized water and 0.44 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (available from Zeolyst as CBV720) to produce a synthesis mixture having the following composition in terms of molar ratios:50 H2O : 1 SiO2: 0.033 AI2O3 : 0.15 QOH : 0.3 NaOH

[0114] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 8 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0115] XRD analysis of the as-synthesized product, illustrated in Figure 2, showed the material to be pure EMM-73. SEM images of the as-synthesized product, illustrated in Figure 3, indicated that the EMM-73 crystals have a rectangular- like morphology with a maximal particle size of less than 1 micron, i.e., about 100-800 nm. ICP elemental analysis indicated a Si / Al ratio of 12.5.Synthesis of EMM-73 in hydroxide media, SDA1 Si / Al 15

[0116] This example was conducted in the same conditions as Example 2 except that NaOH was replaced by RbOH in a Rb / Si amount of 0. 15 to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.033 A12O3: 0.15 QOH : 0.15 RbOH

[0117] After 8 days of heating at 160°C, pure EMM-73 material was obtained, as identified by its XRD pattern.Synthesis of EMM-73 in hydroxide media, SDA1 Si / Al 250, Si / B 20

[0118] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 3.1 g of l,5-diethyl-5-azaindolium cation (Q) as structure directing agent (hydroxide form, 7.2 wt% solution), 0.024 g H3BO3 (100 wt%), 0.22 g of KOH solution (20 wt%), 0.43 g of deionized water and 0.46 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 250 (available from Zeolyst as HSZ-390HUA) to produce a synthesis mixture having the following composition in terms of molar ratios:25 H2O : 1 SiO2: 0.002 A12O3: 0.025 B2O3: 0.15 QOH : 0.1 KOH

[0119] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 12 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0120] XRD analysis of the as-synthesized product, illustrated in Figure 4, showed the material to be pure EMM-73. SEM images of the as-synthesized material, illustrated in Figure 5, indicated that the EMM-73 crystals are in the form of aggregates of crystals having a platelike morphology with a maximal individual particle size of less than 0.2 micron, i.e., about 100-200 nm.Synthesis of EMM-73 in hydroxide media, SDA2, Si / Al 15

[0121] This example was conducted in similar conditions as Example 2 except that SDA1 was replaced with l-ethyl-5-propyl-5-azaindolium cation (SDA2) and that NaOH was used in a smaller Na / Si amount of 0.2 to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.033 A12O3: 0.15 QOH : 0.2 NaOH

[0122] After 12 days of heating at 160°C, pure EMM-73 material was obtained, as identified by its XRD pattern.Synthesis of EMM-73 in hydroxide media, SDA3, Si / Al 15

[0123] This example was conducted in similar conditions as Example 2 except that SDA1 was replaced with l-propyl-5-ethyl-5-azaindolium cation (SDA3) and that NaOH was used in a smaller Na / Si amount of 0.15 to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.033 A12O3: 0.15 QOH : 0.15 NaOH

[0124] After 14 days of heating at 160°C, pure EMM-73 material was obtained, as identified by its XRD pattern.Synthesis of EMM-73 in hydroxide media, SDA4, Si / Al 250, Si / B 15In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together:2.22 g of l,4-diethyl-4-azaindolium cation (Q) as structure directing agent (hydroxide form, 9.4 wt% solution), 0.77 g H3BO3 (3.87 wt%), 0.29 g of NaOH solution (10 wt%), 0.85 g of deionized water and 0.46 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 250 (available from Zeolyst as HSZ-390HUA) to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.002 AhOr : 0.033 B2O3 : 0.15 QOH : 0.1 NaOH

[0126] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 12 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried.

[0127] The as-synthesized product was identified as pure EMM-73 based on its XRD patten.Synthesis of EMM-73 in hydroxide media, SDA5 Si / Al 15

[0128] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 2.73 g of 5,5’-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 12 wt% solution), 0.51 g of NaOH solution (10 wt%), 1.7 g of deionized water and 0.6 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (available from Zeolyst as CBV720) to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiOr : 0.033 AI2O3 : 0.1 Q(OH)2: 0.15 NaOH

[0129] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 18 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized waterand dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0130] XRD analysis of the as-synthesized product showed the material to be pure EMM-73.Synthesis of EMM-73 in hydroxide media, SDA6, Si / Al 15

[0131] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together:2.03 g of 5,5’-(hexane-l ,6-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 13 wt% solution), 0.51 g of NaOH solution (10 wt%), 2.34 g of deionized water and 0.6 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15(available from Zeolyst as CBV720) to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.033 A12O3: 0.075 Q(OH)2: 0.15 NaOH

[0132] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 14 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0133] XRD analysis of the as-synthesized product, as illustrated by Figure 6, showed the material to be pure EMM-73. SEM images of the as-synthesized material, illustrated in Figure7, indicated that the EMM-73 crystals have a rectangular-like morphology with a maximal particle size of about 100 nm.Synthesis of EMM-73 in hydroxide media, SDA6, Si / Al 30a PTFE liner for a 10 mL Steel Parr autoclave, the following were mixed together:7.71 g of 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 13 wt% solution) and 0.62 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 30 (available from Zeolyst as CBV760) to produce a synthesis mixture having the following composition in terms of molar ratios:10 H2O : 1 SiO2: 0.0167 A12O3: 0.25 Q(OH)2

[0135] The liner was then capped, sealed within a 10 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 14 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized waterand dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0136] XRD analysis of the as-synthesized product showed the material to be pure EMM-73.Synthesis of EMM-73 in hydroxide media, SDA6, Si / Al 50

[0137] This example was conducted in similar conditions as Example 1 1 except thatUltrastable Y (USY) zeolite with a Si / Al molar ratio of 50 (available from Tosoh as HSZ-385HUA) was used, to produce a synthesis mixture having the following composition in terms of molar ratios:10 H2O : 1 SiO2: 0.01 A12O3: 0.25 Q(OH)2

[0138] After 14 days of heating at 160°C, pure EMM-73 material was obtained, as identified by its XRD pattern.Synthesis of EMM-73 in hydroxide media, SDA6, Si / Al 33a PTFE liner for a 10 mL Steel Parr autoclave, the following were mixed together: 2.8 g of 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 13 wt% solution), 0.013 g Al(0H)3 (Sigma, 54 wt% AI2O3), 0.52 g ofNaCl solution (10 wt%) and 0.27 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 250 (available from Tosoh as HUA390) to produce a synthesis mixture having the following composition in terms of molar ratios:50 H2O : 1 SiO2: 0.015 A12O3: 0.2 Q(OH)2: 0.2 NaCl

[0140] The liner was then capped, sealed within a 10 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 12 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried. The as-synthesized material was then calcined to 600°C in air within a box furnace with a ramping rate of 3°C / minute. The temperature remained at 600°C for 8 hours and then the box furnace was allowed to cool.

[0141] XRD analysis of the as-synthesized product, as illustrated by Figure 8, showed the material to be pure EMM-73. SEM images of the as-synthesized material, illustrated in Figure 9, indicated that the EMM-73 material is in the form of extra small particles with a maximal size of about 50 nm or less.Synthesis of EMM-73 in hydroxide media, SDA9, Si / Al 15

[0142] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 2.7 g of 5,5’-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 8.7 wt% solution), 0.6 g of NaOH solution (10 wt%), 0.93 g of water and 0.52 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 15 (available from Zeolyst as CBV720) to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.033 AI2O3 : 0.075 Q(OH)2: 0.2 NaOH

[0143] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 14 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried at 90 °C in a vented drying oven.

[0144] XRD analysis of the as-synthesized product showed the material to be pure EMM- 73.Example 15: Synthesis of EMM-73 in hydroxide media, SDA10, Si / Al = 15

[0145] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 2.7 g of 5,5’-(octane-l,8-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 9.2 wt% solution), 0.86 g of NaCl solution (10 wt%), 0.21 g of deionized water, 0.028 g Al(0H)3 (Sigma, 54 wt% AI2O3), and 0.27 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 250 (available from Tosoh as HUA390) to produce a synthesis mixture having the following composition in terms of molar ratios:50 H2O : 1 SiO2: 0.033 AI2O3 : 0.167 Q(OH)2: 0.33 NaCl

[0146] The liner was then capped, sealed within a 23 mL Parr autoclave, and placed within a spit inside of a convection over. The reactor was heated at 160°C for 14 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water and dried at 90 °C in a vented drying oven.

[0147] XRD analysis of the as-synthesized product showed the material to be pure EMM- 73.Example 16: Synthesis of EMM-73 in fluoride media, SDA2, Si / Al = 50

[0148] A mixture of 1.2 g of tetraethylorthosilicate (TEOS, > 99 wt%) and 0.023 g of Al(OiPr)3 (Sigma, 99 wt%) was hydrolyzed at room temperature in l-ethyl-5-propyl-5- azaindolium cation (Q) as structure directing agent (hydroxide form, 8.4 wt% solution) for about 2-3 hours, then 0.12 mL HF (48 wt% solution) was added to the mixture. The gel wasleft at room temperature for a few days to remove the ethanol and water, to produce a synthesis mixture having the following composition in terms of molar ratios:4 H2O : 1 SiO2: 0.01 AI2O3 : 0.5 QOH : 0.5 HF

[0149] The thick paste was homogenized by hand in a PTFE container and transferred to a 23 mL PTFE-lined stainless steel Parr autoclave. The autoclave was kept at 160°C with rotation (about 40 rpm) for 21 days in a convection oven. The product was isolated by filtration, rinsed with deionized water and dried at 90°C in a vented drying oven.

[0150] XRD analysis of the as-synthesized product showed the material to be pure EMM- 73. SEM images of the as-synthesized material, illustrated in Figure 10, indicated that the EMM-73 crystals have a rectangular-like morphology with a maximal particle size of about 300 nm or less.Synthesis of EMM-73 in fluoride media, SDA7, Si / Al 33

[0151] 2.36 g of tetraethylorthosilicate (TEOS, > 99 wt%) and 0.0323 g of aluminium hydroxide (Al(0H)3, Sigma 54 wt% AI2O3) were hydrolyzed at room temperature in 13.6 g of 5,5’-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 8.3 wt% solution) for about 2-3 hours. The mixture was then heated at about 50°C to remove the ethanol and water. 0.24 g HF (48 wt% solution) were added to the mixture to produce a synthesis mixture having the following composition in terms of molar ratios:5 H2O : 1 SiO2: 0.015 AI2O3 : 0.25 Q(OH)2: 0.5 HF

[0152] The resulting thick paste was homogenized by hand in a PTFE container and transferred to a 10 mL PTFE-lined stainless steel Parr autoclave. The autoclave was kept at 160°C for 21 days in a tumbling oven (about 40 rpm). After 21 days, the reactor was discharged and the product was collected using centrifugation and washing three times with distilled water (100 mL). The product was dried at 90°C in a vented drying oven.

[0153] XRD analysis of the as-synthesized product, illustrated in Figure 1 1, showed the material to be pure EMM-73. SEM images of the as-synthesized material, illustrated in Figure12, indicated that the EMM-73 crystals have a rectangular-like morphology with a maximal particle size of about 300 nm or less.Synthesis of EMM-73 in fluoride media, SDA8, Si / Al 33

[0154] This example was conducted in similar conditions as example 17, except that 5,5’- (butane-l,4-diyl)bis(l-ethyl-5-azaindolium) cation (Q) was used as structure directing agent (hydroxide form, 11 wt% solution).

[0155] After 21 days at 160°C, pure EMM-73 material was obtained, as identifed by its XRD pattern.Example 19: Synthesis of EMM-73 in fluoride media, SDA9, silicate

[0156] A mixture of 1.2 g of tetraethylorthosilicate (TEOS, > 99 wt%) was hydrolyzed at room temperature in 5,5’-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium) cation (Q) as structure directing agent (hydroxide form, 8.7 wt% solution) for about 2-3 hours, then 0.12 mL HF (48 wt% solution) was added to the mixture. The gel was left at room temperature for a few days to remove the ethanol and water, to produce a synthesis mixture having the following composition in terms of molar ratios:5 H2O : 1 SiO2: 0.5 QOH : 0.5 HF

[0157] The thick paste was homogenized by hand in a PTFE container and transferred to a 23 mL PTFE-lined stainless steel Parr autoclave. The autoclave was kept at 160°C with rotation (about 40 rpm) for 14 days in a convection oven. The product was isolated by filtration, rinsed with deionized water and dried at 90 °C in a vented drying oven.

[0158] XRD analysis of the as-synthesized product showed the material to be pure EMM- 73.

[0159] While the present invention has been described and illustrated with reference to particular embodiments, it will be appreciated by those of ordinary skill in the art that the invention lends itself to many different alterations, modifications, and variations not specifically illustrated herein. It will also be apparent to those skilled in the art that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. Also, all numerical values within the detailed description herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0160] Where in the foregoing description, integers or elements are mentioned which have known, obvious or foreseeable equivalents, then such equivalents are herein incorporated as if individually set forth. Reference should be made to the claims for determining the true scope of the present invention, which should be construed so as to encompass any such equivalents. It will also be appreciated by the reader that integers or features of the invention that are described as preferable, advantageous, convenient or the like are optional and do not limit the scope of the independent claims. Moreover, it is to be understood that such optional integers or features, whilst of possible benefit in some embodiments of the invention, may not be desirable, and may therefore be absent, in other embodiments.

[0161] Additionally or alternately, the invention relates to:

[0162] Embodiment 1 : A method of making EMM-73 molecular sieve in hydroxide media, comprising the steps of:(a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), a source of an oxide of tri valent element (X), a structure directing agent (Q), a source of hydroxide ions (OH), and optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4- azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquatemary cations of Formula III as defined above, where R is selected from methyl, ethyl, and n-propyl, R’ is selected from methyl, ethyl and n-propyl, and n is 4 to 10, and wherein, if Y is Si, X is Al, the structure directing agent (Q) is 1,5-diethyl- 5-azaindolium or 1 -propyl-5-methyl-5-azaindolium, and in the absence of seed crystals, an alkali and / or alkaline earth metal element (M) is present in a M / OH molar ratio of more than 0.5;(b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve; and(c) recovering at least a portion of the molecular sieve from step (b).

[0163] Embodiment 2: The method of embodiment 1, further comprising step (d) of treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

[0164] Embodiment 3: The method of embodiment 1 or 2, wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, where R and R’ are independently selected from methyl, ethyl, and n-propyl, in particular wherein R and R’ are ethyl.

[0165] Embodiment 4: The method of embodiment 1 or 2, wherein the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium monoquatemary cations of Formula II, where R and R’ are independently selected from methyl, ethyl, and n-propyl, in particular wherein R is selected from ethyl and n-propyl, and R’ is selected from methyl, ethyl and n-propyl.

[0166] Embodiment 5: The method of embodiment 1 or 2, wherein the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium diquatemary cations of Formula III, where R is selected from methyl, ethyl, and n-propyl, in particular methyl or ethyl, and n is 4 to 10, preferably 4 to 8, more preferably 6 to 8.

[0167] Embodiment 6: The method of embodiment 1 or 2, wherein the structure directing agent (Q) comprises at least one cation selected from l,4-diethyl-4-azaindolium, 1,5-diethyl- 5-azaindolium, l-ethyl-5-propyl-5-azaindolium, l-propyl-5-methyl-5-azaindolium, 1-propyl- 5 -ethyl- 5 - azaindolium, 5 , 5 ' -(octane- 1 , 8 -diyl)bis( 1 -methyl- 5 - azaindolium) , 5,5' -(octane- 1,8- diyl)bis(l-ethyl-5 -azaindolium), 5,5'-(heptane-l,7-diyl)bis(l-methyl-5-azaindolium), 5,5'- (heptane-l,7-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(hexane-l,6-diyl)bis(l-methyl-5- azaindolium), 5,5'-(hexane-l,6-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l- methyl-5 -azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(butane-l,4- diyl)bis(l-methyl-5-azaindolium), or 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium).

[0168] Embodiment 7: The method of embodiment 1 or 2, wherein the structure directing agent (Q) comprises at least one cation selected from l,4-diethyl-4-azaindolium, 1,5-diethyl- 5-azaindolium, l -ethyl-5-propyl-5-azaindolium, 1 -propyl-5-methyl-5-azaindolium, 1 -propyl- 5 -ethyl- 5 -azaindolium, 5,5'-(octane-l,8-diyl)bis(l-methyl-5-azaindolium), 5,5'-(heptane-l,7- diyl)bis(l-ethyl-5 -azaindolium), 5,5'-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium), and 5,5'- (hexane-l,6-diyl)bis(l-ethyl-5-azaindolium).

[0169] Embodiment 8: The method of any one of the preceding embodiments, wherein the structure directing agent (Q) is in the form of a halide, hydroxide or nitrate, preferably wherein the structure directing agent (Q) is in its hydroxide form.

[0170] Embodiment 9: The method of any one of the preceding embodiments, wherein the synthesis mixture has the following composition in terms of molar ratios:Molar ratios Typical range Preferred range More preferred rangeY / X 5 - 500 5 - 100 8 - 50Q / Y 0.01 - 1.0 0.05 - 0.8 0.1 - 0.7OH / Y 0.05 - 1.5 0.1 - 1.0 0.2 - 0.8M / Y 0 - 1.0 0.05 - 0.7 (if present) 0.08 - 0.5 (if present)H2O / Y 1 - 100 10 - 70 15 - 50

[0171] Embodiment 10: A method of making EMM-73 molecular sieve in fluoride media, comprising the steps of:(a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), optionally a source of an oxide of bivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), optionally a source ofalkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquaternary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III as defined above, where R is selected from methyl, ethyl, and n-propyl, in Formula I R’ is selected from methyl, ethyl and n-propyl, in Formula II R’ is methyl or n- propyl, and n is 4, 5, 7, 9 or 10,(b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve; and(c) recovering at least a portion of the molecular sieve from step (b).

[0172] Embodiment 11: The method of embodiment 10, further comprising step (d) of treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

[0173] Embodiment 12: The method of embodiment 10 or 11, wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquaternary cations of Formula I, where R and R’ are independently selected from methyl, ethyl, and n- propyl, in particular wherein R and R’ are ethyl.

[0174] Embodiment 13: The method of embodiment 10 or 11, wherein the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium monoquaternary cations of Formula II, where R is selected from methyl, ethyl, and n-propyl, and R’ is selected from methyl and n-propyl, in particular wherein R is selected from ethyl and n-propyl, and R’ is selected from methyl and n-propyl.

[0175] Embodiment 14: The method of embodiment 10 or 11, wherein the structure directing agent (Q) comprises at least one cation selected from 5-azaindolium diquatemary cations of Formula III, where R is selected from methyl, ethyl, and n-propyl, in particular ethyl, and n is 4, 5, 7, 9 or 10, preferably 4, 5 or 7.

[0176] Embodiment 15: The method of embodiment 10 or 11, wherein the structure directing agent (Q) comprises at least one cation selected from l,4-diethyl-4-azaindolium, 1- ethyl-5-propyl-5-azaindolium, 5,5’-(heptane-l,7-diyl)bis(l-methyl-5-azaindolium), 5,5’- (heptane-l,7-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-methyl-5- azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(butane-l,4-diyl)bis(l- methyl-5-azaindolium), or 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium).

[0177] Embodiment 16: The method of embodiment 10 or 11, wherein the structure directing agent (Q) comprises at least one cation selected from l-ethyl-5-propyl-5-azaindolium,5,5'-(heptane-l,7-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-ethyl-5- azaindolium), and 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium).

[0178] Embodiment 17: The method of any one of embodiments 10 to 16, wherein the structure directing agent (Q) is in the form of a halide, hydroxide or nitrate, preferably wherein the structure directing agent (Q) is in its hydroxide form.

[0179] Embodiment 18: The method of any one of embodiments 10 to 17, wherein the synthesis mixture has the following composition in terms of molar ratios:Molar ratios Typical range Preferred range More preferred rangeY / X 5 - 500 5 - 100 8 - 50Q / Y 0.01 - 1.0 0.05 - 1.0 0.2 - 0.8F / Y 0.05 - 2.0 0.1 - 1.5 0.2 - 1.0OH / Y 0 - 1.5 0.1 - 1.0 (if present) 0.2 - 0.8 (if present)M / Y 0 - 1.0 0.01 - 0.5 (if present) 0.01 - 0.2 (if present)H2O / Y 1 - 50 2 - 30 3 - 15

[0180] Embodiment 19: The method of any one of the preceding embodiments, wherein Y comprises one or more of silicon, titanium and germanium, preferably Y comprises or is silicon.

[0181] Embodiment 20: The method of any one of the preceding embodiments, wherein X comprises one or more of aluminum, boron, iron and gallium, preferably X comprises or is aluminum and / or boron.

[0182] Embodiment 21 : An EMM-73 molecular sieve having at least one of 4-azaindolium monoquatemary cations of Formula I, 5 -azaindo lium monoquaternary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III within its pore structure.

[0183] Embodiment 22: The EMM-73 molecular sieve of embodiment 21, having at least one cation selected from 1 ,4-diethyl-4-azaindolium, l,5-diethyl-5-azaindolium, l-ethyl-5- propyl-5-azaindolium, l-propyl-5-methyl-5-azaindolium, l-propyl-5-ethyl-5-azaindolium, 5,5'-(octane-l,8-diyl)bis(l-methyl-5-azaindolium), 5,5’-(octane-l,8-diyl)bis(l-ethyl-5- azaindolium), 5,5'-(heptane-l,7-diyl)bis(l-methyl-5-azaindolium), 5,5'-(heptane-l,7- diyl)bis(l-ethyl-5-azaindolium), 5,5'-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium), 5,5'- (hexane-l,6-diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-methyl-5- azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium), 5,5’-(butane-l,4-diyl)bis(l-methyl-5-azaindolium), and 5,5'-(butane-l,4-diyl)bis(l-ethyl-5-azaindolium) within its pore structure.

[0184] Embodiment 23: An EMM-73 molecular sieve obtainable by the method of any one of embodiments 1 to 20.

[0185] Embodiment 24: An EMM-73 molecular sieve, such as the EMM-73 molecular sieve of any one of embodiments 21 to 23, having a Y / X molar ratio higher than 100, as determined by ICP.

[0186] Embodiment 25: The EMM-73 molecular sieve of any one of embodiments 21 to 24, having an average maximal particle size of less than 2 microns, in particular of less than 1 micron, as determined by scanning electron microscopy (SEM).

[0187] Embodiment 26: An EMM-73 molecular sieve, such as the EMM-73 molecular sieve of any one of embodiments 21 to 24, having an average maximal particle size of less than 100 nm, preferably of less than 75 nm, more preferably of less than 50 nm, as determined by scanning electron microscopy (SEM).

[0188] Embodiment 27: The EMM-73 molecular sieve of any one of embodiments 21 to26, wherein at least a portion of the molecular sieve has a plate-like or a rectangular-like morphology.

[0189] Embodiment 28: The EMM-73 molecular sieve of any one of embodiments 21 to27, wherein the molecular sieve is a silicate, a borosilicate, an aluminosilicate, or an aluminoborosilicate.

[0190] Embodiment 29: A process of converting an organic compound to a conversion product, which comprises contacting the organic compound with the EMM-73 molecular sieve of any one of embodiments 21 to 28.

Claims

CLAIMS1. A method of making EMM-73 molecular sieve in hydroxide media, comprising the steps of: (a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of hydroxide ions (OH), and optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquaternary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquatemary cations of Formula III:Formula III where R is selected from methyl, ethyl, and n-propyl, R’ is selected from methyl, ethyl and n- propyl, and n is 4 to 10, and wherein, if Y is Si, X is Al, the structure directing agent (Q) is 1,5- diethyl-5-azaindolium or l-propyl-5-methyl-5-azaindolium, and in the absence of seed crystals, an alkali and / or alkaline earth metal element (M) is present in a M / OH molar ratio of more than 0.5; (b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve; (c) recovering at least a portion of the molecular sieve from step (b); and (d) optionally treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

2. The method of claim 1, wherein the structure directing agent (Q) comprises at least one cation selected from 1 ,4-diethyl-4-azaindolium, l,5-diethyl-5- azaindolium, l-ethyl-5-propyl-5-azaindolium, l-propyl-5-methyl-5-azaindolium, l-propyl-5- ethyl-5-azaindolium, 5,5'-(octane-l ,8-diyl)bis(l-methyl-5-azaindolium), 5,5'-(heptane-l,7- diyl)bis(l-ethyl-5-azaindolium), 5,5'-(hexane-l,6-diyl)bis(l-methyl-5-azaindolium) cation, and 5,5’-(hexane-l,6-diyl)bis(l-ethyl-5-azaindolium).

3. The method of claim 1 or 2, wherein the structure directing agent (Q) is in the form of a halide, hydroxide or nitrate, preferably wherein the structure directing agent (Q) is in its hydroxide form.

4. The method of any one of claims 1 to 3, wherein the synthesis mixture has the following composition in terms of molar ratios:Molar ratios Typical range Preferred range More preferred range5 - 100 8 - 50 1.0 0.05 - 0.8 0.1 - 0.7 1.5 0.1 - 1.0 0.2 - 0.80.05 - 0.7 (if present) 0.08 - 0.5 (if present)10 - 70 15 - 505. A method of making EMM-73 molecular sieve in fluoride media, comprising the steps of: (a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), optionally a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), wherein the structure directing agent (Q) comprises at least one cation selected from 4-azaindolium monoquatemary cations of Formula I, 5-azaindolium monoquatemary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III:Formula III where R is selected from methyl, ethyl, and n-propyl, in Formula I R’ is selected from methyl, ethyl and n-propyl, in Formula II R’ is methyl or n-propyl, and n is 4, 5, 7, 9 or 10, (b) heating said synthesis mixture under crystallization conditions including a temperature of from 100 to 200°C for a time sufficient to form crystals of said molecular sieve; (c) recovering at least a portion of the molecular sieve from step (b); and (d) optionally treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

6. The method of claim 5, wherein the structure directing agent (Q) comprises at least one cation selected from l-ethyl-5-propyl-5-azaindolium, 5,5’-(heptane-l,7- diyl)bis(l-ethyl-5-azaindolium), 5,5'-(pentane-l,5-diyl)bis(l-ethyl-5-azaindolium), and 5,5'- (butane- 1 ,4-diyl)bis( 1 -ethyl-5 -azaindolium).

7. The method of claim 5 or 6, wherein the structure directing agent (Q) is in the form of a halide, hydroxide or nitrate, preferably wherein the structure directing agent (Q) is in its hydroxide form.

8. The method of any one of claims 5 to 7, wherein the synthesis mixture has the following composition in terms of molar ratios:Molar ratios Typical range Preferred range More preferred rangeY / X5 - 500 5 - 100 8 - 50Q / Y0.01 - 1.0 0.05 - 1.0 0.2 - 0.8F / Y0.05 - 2.0 0.1 - 1.5 0.2 - 1.0OH / Y 0 - 1.5 0.1 - 1.0 (if present) 0.2 - 0.8 (if present)M / Y 0 - 1.0 0.01 - 0.5 (if present) 0.01 - 0.2 (if present)H2° / Y1 - 50 2 - 30 3 - 159. An EMM-73 molecular sieve having at least one of 4-azaindolium monoquatemary cations of Formula I, 5 -azaindolium monoquaternary cations of Formula II, and 5-azaindolium diquaternary cations of Formula III within its pore structure.

10. An EMM-73 molecular sieve obtainable by the method of any one of claims 1 to 8.

11. An EMM-73 molecular sieve having a Y / X molar ratio higher than 100, as determined by ICP.

12. The EMM-73 molecular sieve of any one of claims 9 to 11, having an average maximal particle size of less than 2 microns, in particular of less than 1 micron, as determined by scanning electron microscopy (SEM).

13. An EMM-73 molecular sieve having an average maximal particle size of less than 100 nm, preferably of less than 75 nm, more preferably of less than 50 nm, as determined by scanning electron microscopy (SEM).

14. The EMM-73 molecular sieve of any one of claims 9 to 13, wherein at least a portion of the molecular sieve has a plate-like or a rectangular-like morphology.

15. A process of converting an organic compound to a conversion product, which comprises contacting the organic compound with the EMM-73 molecular sieve of any one of claims 9 to 14.

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