Methods of making molecular sieves of *MRE framework type

Abstract

The present disclosure relates to a method of making molecular sieves of *MRE framework type, in particular a method using a 1,2-dimethylimidazo[1,2-a]pyridin-1-ium cation as structure directing agent. The method can allow for formation of molecular sieves of *MRE framework type in various synthesis mixture environments, with the resulting molecular sieves having a wide variety of silica to alumina ratios.

Description

METHODS OF MAKING MOLECULAR SIEVES OF *MRE FRAMEWORK TYPEFIELD OF THE INVENTION

[0001] The present disclosure relates to methods of making molecular sieves of *MRE framework type, in particular a method using a l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation as structure directing agent.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 least silicon and oxygen atoms that are alternately bonded to each other (i.e., -O-Si-O-Si-), and optionally including other atoms within the inorganic framework structure, including atomssuch 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, and SFS framework type zeolites, e.g. , mazzite, offretite, zeolite L, zeolite Y, zeolite X, omega, ZSM-2, ZSM-12, zeolite T, Beta, and SSZ-56. Large pore zeolites generally have a free pore diameter of 0.6 to 0.8 nm. Medium (or intermediate) pore size zeolites (10R) include, for example, MFI, MEL, *MRE, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites, e.g., ZSM-5, ZSM-11, ZSM-48, ZSM-22, ZSM-23, ZSM-35, MCM-22, silicalite-1 , and silicalite-2. Medium pore size zeolites generally have a free pore diameter of 0.45 to 0.6 nm. Small pore size zeolites (8R) include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework type zeolites, e.g., ZK-4, SAPO-34, SAPO-35, ZK-14, S APO-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 molecular sieve materials typically involves hydrothermal crystallization from a synthesis mixture comprising sources of all the elements present in the molecular sieve (or 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 molecular sieves and which are thought to act as templates around which certain 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, molecular sieve (or zeolite) crystals form around structure directing agents with the structure directing agent occupying pores in the molecular sieve once crystallization is complete. The “as-synthesized” (or “as-made”) molecular sieve will therefore contain the structure directing agent in its pores so that, following crystallization, the “as-synthesized” molecular sieve is usually subjected to a treatment step such as a calcination step to remove the structure directing agent.

[0009] One type of zeolite structure used for catalytic processing of petroleum streams is ZSM-48, which has orthorhombic or pseudo-orthorhombic symmetry and ten-ring noninterconnecting, linear channels (or one-dimension 10-ring tubular pore system) whose ideal dimensions are 5.5 x 5.6 A. The framework structure of ZSM-48 has been assigned the three- letter code *MRE. According to R.F. Lobo etal. (J. Am. Chem. Soc., 2002, 124, 13222-13230), ZSM-48 is not a code for one material but for a family of materials with different degrees of disorder, corresponding to various polytypes. As a result, molecular sieves of the *MRE framework type can comprise zeolites of the ZSM-48 family such as at least one of COK-8, EU-2, EU-1 1, IZM-1, SSZ-91, ZBM-30, RUB-58, and ZSM-48.

[0010] As for many zeolites, the composition of the synthesis mixture used to form ZSM- 48 (or other *MRE framework type molecular sieves) can have a strong impact on the crystalline structure and / or morphology of the resulting zeolites.

[0001] ZSM-48 was first synthesized by Rollmann et al. using a C4 to C12 organic diamine as a structure-directing agent, see U.S. Patent No. 4,423,021. As synthesized by Rollman et al., the zeolite contained little or no aluminum.

[0011] U.S. Patent No. 6,923,949 describes methods for forming ZSM-48 crystals using synthesis mixtures that include at least one organic template material selected from organiclinear diquaternary alkyl ammonium compounds, e.g., hexamethonium chloride, and linear diamino alkanes, and non-ZSM-48 seed crystals. The resulting ZSM-48 crystals can have an X-ray diffraction pattern corresponding to ZSM-48, although the presence of the non-ZSM-48 seed crystals can be detected based on activity tests. For crystals having a silica to alumina ratio of about 70 to 1 to 150 to 1, the ZSM-48 crystals formed using non-ZSM-48 seeds are described as being small, irregularly shaped crystals that are free from fibrous morphology. For crystals with a silica to alumina ratio of less than 70 to 1 , the ZSM-48 crystals are described as being mixtures of small, irregularly shaped crystals and needle morphology crystals.

[0002] U.S. Patent No. 7,482,300 describes methods for forming ZSM-48 crystals without the use of non-ZSM-48 seeds in the synthesis mixture. The structure directing agent used for forming the ZSM-48 crystals is described as a hexamethonium salt, such as hexamethonium chloride. The resulting crystals can have a silica to alumina ratio from about 70 to 1 to about 110 to 1 , and are described as being substantially free of fibrous morphology. Preferred ranges are also described for the molar ratio of OH" to SiO2 and the molar ratio of structure directing agent (or template) to SiO2. The preferred ranges are described as suitable for formation of crystals that are substantially free of needle-like morphology crystals.

[0003] U.S. Patent No. 8,003,074 describes methods for forming ZSM-48 crystals using a diquaternary ammonium salt structure directing agent with a 5 carbon atom alkyl chain between the ammonium ions (a “diquat-5” structure directing agent). Synthesis of ZSM-48 crystals using mixtures of a “diquat-5” structure directing agent and other structure directing agents, such as a “diquat-6” structure directing agent, is also described. Various types of synthesis mixtures are described that result in formation of fibrous and / or needle-like crystal morphologies.

[0004] U.S. Patent No. 9,873,614 describes methods for forming substantially pure phase ZSM-48 crystals having a fiber or needle morphology, using synthesis mixtures containing non-sodium alkali metal ions and a diquatemary alkylammonium salt structure directing agent with a 6 carbon atom alkyl chain between the ammonium ions (“diquat-6”). The desired morphology can be achieved in part by reducing, minimizing, and / or eliminating the presence of sodium ions in the synthesis mixture.

[0005] U.S. Patent No. 9,802,830 describes methods for forming molecular sieve SSZ-91, a molecular sieve belonging to the ZSM-48 family of molecular sieves, having a silicon oxide to aluminum oxide mole ratio of 40 to 200 and a morphology in the form of polycrystallineaggregates of low aspect ratio crystallites, using hexamethonium cations as structure directing agent.

[0006] Molecular sieves of *MRE framework type, such as ZSM-48, have shown attractive properties as a catalyst, for instance for the dewaxing of hydrocarbon feedstocks, see for example U.S. Patent Nos. 5,075,269, 6,884,339 and 6,984,309.

[0007] As a result, there is considerable interest in finding new methods of synthesizing *MRE molecular sieves, such as ZSM-48.SUMMARY OF THE INVENTION

[0012] According to the present invention, it has now been found that molecular sieves of *MRE framework type can be synthesized using l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation as structure directing agent. This new method is advantageous as it allows for the preparation of aluminosilicate or silicate molecular sieves of *MRE framework type, e.g., ZSM-48, with a wide range of silica to alumina ratio (such as from 60 to infinity), under both hydroxide and fluoride media. The present inventors have also found that the use of 1 ,2- dimethylimidazo[l,2-a]pyridine-l-ium cation as structure directing agent allows for the preparation of aluminosilicate or silicate molecular sieves of *MRE framework type, e.g., ZSM-48, with a lower tendency to produce impurity phase (such as EUO) than structure directing agents traditionally used for the synthesis of molecular sieves of *MRE framework type such as hexamethonium or pentamethonium cations.

[0008] In a first aspect, the present disclosure therefore relates to a method of making a molecular sieve of *MRE framework type, comprising the following steps:(a) preparing a synthesis mixture comprising water, at least one source of silica, optionally at least one source of alumina, a structure directing agent (Q) comprising at least one l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation, a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), and optionally a source of fluoride ions (F), wherein the synthesis mixture comprises Si and Al in a Si / Al molar ratio of at least 30;(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).

[0009] In a second aspect, the present disclosure relates to a molecular sieve of *MRE framework type obtainable by (or obtained by) the method of the present disclosure.

[0010] In a third 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 *MRE framework type, e.g., ZSM-48, obtainable by (or obtained by) the method of the present disclosure, in a hydrocarbon chemical conversion process.

[0011] 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 invention may be incorporated into other aspects of the present invention. In particular, any two or more of the features described in this specification, including in this summary section, can be combined to form combinations of features not specifically described herein.DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 shows the powder XRD pattern of the as-synthesized material of Example 2.

[0013] Figure 2 shows the powder XRD pattern of the calcined material of Example 2.

[0014] Figure 3 shows a SEM image of the as-synthesized material of Example 2.

[0015] Figure 4 shows the powder XRD pattern of the as-synthesized material of Example 3.

[0016] Figure 5 shows the powder XRD pattern of the calcined material of Example 3

[0017] Figure 6 shows a SEM image of the as-synthesized material of Example 1 .

[0018] Figure 7 shows molar ratios and conditions used for the syntheses of Examples 2 to 12.

[0019] Figure 8 shows molar ratios and conditions used for the syntheses of Examples 13 to 20.DETAILED DESCRIPTION OF THE INVENTION

[0020] Described herein are methods of making molecular sieves of *MRE framework.

[0021] As used herein, molecular sieves of *MRE framework type comprise zeolites of the ZSM-48 family such as at least one of COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, RUB- 58, and ZSM-48. In the following, the expressions “zeolite” and “molecular sieve” can be used interchangeably. Also, the expression “ZSM-48 family” is used synonymously with theexpression “molecular sieve of *MRE framework type”. The term “ZSM-48 family” material as used herein, includes one or more of:- molecular sieves made from a common first degree crystalline building block unit cell, which unit cell has the *MRE framework topology (A unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure. Such crystal structures are discussed in the “Atlas of Zeolite Framework Types,” Fifth edition, 2001 , the entire content of which is incorporated as reference);- molecular sieves made from a common second degree building block, being a 2-dimensional tiling of such *MRE framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;- molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness. The stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; and- molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the *MRE framework topology.

[0022] More particularly, molecular sieves of *MRE framework type comprise a family of materials having straight channels (or tubular) pores. The pores are formed of rolled up honeycomb- like sheets of fused T6-rings (T= tetrahedral), and the pore aperture contains 10 T- atoms. Neighbouring pores are related by a zero shift along the pore direction or by a shift of half the repeat distance along the pore direction. Molecular sieves of *MRE framework type generally have an X-ray diffraction pattern including d-spacing maxima at 11.8+0.2, 10.2+0.2, 7.2+0.15, 4.2+0.08, 3.9+0.08, 3.6+0.06, 3.1+0.05 and 2.85+0.05 Angstrom. The X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.

[0023] In a first aspect, the present disclosure relates to a method of making a molecular sieve of *MRE framework type, e.g.. ZSM-48, comprising the following steps:(a) preparing a synthesis mixture comprising water, at least one source of silica, optionally at least one source of alumina, a structure directing agent (Q) comprising at least one l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation, a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), and optionally a sourceof fluoride ions (F), wherein the synthesis mixture comprises Si and Al in a Si / Al molar ratio of at least 30;(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).

[0024] The synthesis mixture comprises at least one source of silica. Suitable sources of silica (e.g., silicon oxide sources) 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 CabO-O-Sil® (available from DMS), precipitated silica such as Ultrasil® and Sipernat® 340 (available from Evonik) or Hi-Sil®, alkali metal silicates such as potassium silicate and sodium silicate, and aqueous colloidal suspensions of silica, for example, that sold by Grace under the tradename Ludox® or that sold by Evonik under the tradename Aerodisp®; preferably silicates, fumed silica, colloidal silica, precipitated silica, and alkali metal silicates, e.g., silicates, colloidal silica or precipitated silica.

[0025] The synthesis mixture optionally comprises at least one source of alumina. Suitable sources of alumina (e.g. , aluminum oxide) 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.

[0026] Alternatively or in addition to previously mentioned sources of silica and alumina, sources containing both Si and Al elements can also be used. 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-TypeZeolite, Ultrastable Y (USY), beta or other large to medium pore molecular sieves or zeolites. Such Si and Al sources are especially suitable in the present method.

[0027] The synthesis mixture may have a Si / Al molar ratio of from 30 to infinity (corresponding to a silicate product), for instance at least 40 or at least 50 or advantageously more than 50. The Si / Al molar ratio in the synthesis mixture may be as high infinity, or up to 500, or up to 300, e.g., up to 250.

[0028] 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 / Si molar ratio of 0.01 to 1.0, such as 0.025 to 1.0, or 0.05 to 0.8, or 0.1 to 0.7, for instance from 0.01, 0.025 or 0.05 to 0.6 or to 0.5, e.g., 0.01, 0.05, 0.15, 0.2, 0.4 or 0.5.

[0029] The synthesis mixture may optionally comprise a second structure directing agent (Q’) selected from structure directing agents traditionally used for the synthesis of molecular sieves of *MRE framework type, such as linear diquatemary alkylammonium structure directing agents. In particular, said second structure directing agent (Q’) may be selected from the group consisting of pentamethonium cation ((CHs NhUH ^N^CHsfi), “Mee-diquat-5 cation”), hexamethonium cation ((CH3)3N+(CH2)eN+(CH3)3), “Mee-diquat-6 cation”), and mixtures thereof. Said second 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 it may be used in its chloride or bromide and / or hydroxide form. When the synthesis mixture comprises a second structure directing agent (Q’), it may present in a Q7Si molar ratio of from 0.01 to 0.5, such as from 0.01 to 0.25 or to 0.1, or be as low as from 0.01 to 0.05 or to 0.04, e.g., 0.02 or 0.03. When the synthesis mixture comprises a second structure directing agent (Q’), the amount of structure directing agent (Q) in the synthesis mixture can advantageously be minimized, for instance, it may be present in a Q / Si molar ratio as low as 0.01 to 0.5, advantageously from 0.01 to 0.1, for instance from 0.01 to 0.05, therefore limiting the costs associated with the synthesis. Also, without wishing to be bound by theory, it is believed that the presence of a second structure directing agent (Q’) in the synthesis mixture may favor the preparation of a molecular sieve of *MRE framework type, as illustrated by very short crystallization times e.g., at most one week, in particular less than one week, or even as short as three days) and / or a higher purity, in particular for synthesis mixtures having a Si / Al molar of 30 to 50 and / or in the absence of seeds.

[0030] 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) and / or of the optional second 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, lithium hydroxide, ammonium hydroxide, and mixtures thereof; most often sodium hydroxide and / or potassium hydroxide. The synthesis mixture may comprise the hydroxide ions source in an OH / Si molar ratio of from 0.01 to 1.5, such as from 0.05 or 0.1 to 1 .0, for instance from 0.1 to 0.8 or 0.7 or 0.6, <?.g., from 0.1 to 0.5.

[0031] Optionally, the synthesis mixture may 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 and / or potassium, more 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 salts 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, 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 / Si molar ratio of from 0 to 1.0, such as (if present) 0.01 to 0.5, for instance 0.025 to 0.4 or to 0.3, e.g., 0.05 to 0.15 or advantageously lower than 0.1. Alternatively, the synthesis mixture may be substantially free from alkali or alkaline earth metal cation (M).Without wishing to be bound by theory, it is believed that the a limited amount of alkali and / or alkaline earth metal cation (M) in the synthesis mixture, if any, such as in a M / Si molar ratio of from 0 to less than 0.1 , for instance from 0.01 to 0.08, e.g., 0 or 0.05 and / or in a M / OH molar ratio amount of less than 0.4, such as 0.3 or less than 0.3, may favor the preparation of molecular sieves of *MRE framework type over other types of frameworks and / or a higher purity, in particular for synthesis mixtures having a Si / Al molar of 30 to 50, in the absence of seeds and of a second structure directing agent (Q’).

[0032] The synthesis mixture may optionally comprise 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 a counter ion of the structure directing agent (Q) and / or of the optional second 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 (SnF2); 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). The fluoride ions (F) may be present in a F / Si molar ratio of from 0 to 1.0, for instance (if present) 0.1 to 0.8, such as 0.2 to 0.7, or 0.3 to 0.6, e.g., 0.5. The addition of fluoride ions is especially advantageous for the preparation of molecular sieves of *MRE framework type from a synthesis mixture having a Si / Al molar ratio higher than 50, such as at least 100 and up to infinity (silicates). Alternatively, the synthesis mixture may be substantially free from a fluoride source.

[0033] 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) and / or of the optional second 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 / Si molar ratio of 0 to 0.2, such as 0 to 0.1, for instance, if present, up to 0.05, e.g., 0.04. Alternatively, the synthesis mixture may be substantially free from halide ions (W).

[0034] The synthesis may be performed with or without added nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds may be of the same or of a different framework type than *MRE, such as seeds of FAU or BEA framework type e.g., Faujasite such as zeolite Y or zeolite X, or Beta zeolite), for instance molecular sieves of *MRE framework type obtained from a previous synthesis. The seeds, if present, may suitably be 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. Without wishing to be bound by theory, it is believed that the presence of nucleating seeds in the synthesis mixture may favor the preparation of a molecular sieve of *MRE framework type, as illustrated by shorter crystallization times and / or a higher purity, in particular for synthesis mixtures having a Si / Al molar of 30 to 50.

[0035] The synthesis mixture typically comprises water in a FFO / Si molar ratio of from 1 to 100, such as 5 to 80 or 5 to 70, for instance 10 to 50 or 10 to 30. 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 silica 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 FFO / Si 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 I FO / Si molar ratio.

[0036] Carbon in the form of CIE may be present in the various sources of components used to prepare the synthesis mixture 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.

[0037] 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).

[0038] The synthesis mixture is then subject to crystallization conditions suitable for the molecular sieve material to form. Crystallization of the molecular sieve material 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.

[0039] 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 or 170°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. 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.

[0040] 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.

[0041] 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, subatmospheric or superatmospheric 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.

[0042] 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-synthesizedmolecular 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 subatmospheric 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.

[0043] The molecular sieve 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.

[0044] The molecular sieve 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.

[0045] In a second aspect, the present disclosure relates to a molecular sieve of *MRE framework type, e.g., ZSM-48, obtainable by (or obtained by) the method of the present disclosure.

[0046] In one or more further embodiments, said molecular sieve of *MRE framework type, may have silica to alumina (SiC^AhCh or Si / AE) molar ratio of from 30 to infinity (corresponding to a silicate product), such as from 30 up to 500, or up to 300, or up to 250, as measured by inductively coupled plasma optical emission spectrometry (ICP-OES).

[0047] In one or more further embodiments, said molecular sieve of *MRE framework type, in its calcined form, may have a BET surface area of from 100 to 500 m2 / g, such as from 200 to 400 m2 / g; e.g., from 250 to 300 m2 / g; and / or a micropore surface area of from 100 to 400 m2 / g, such as from 150 to 300 m2 / g, e.g., from 200 to 250 m2 / g; and / or an external surface area of from 10 to 100 m2 / g, such as from 20 to 60 m2 / g, e.g., from 40 to 50 m2 / g.

[0048] In one or more further embodiments, said molecular sieve of *MRE framework type, in its calcined form, may have a micropore volume ( Vmjcro) of 0.04 to 0.2, for example 0.05 to 0.1 cm3 / g.

[0049] 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 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 molecular sieves of non-*MRE framework type co-existing with the *MRE molecular sieve of the present disclosure are, e.g., Kenyaite, Magadiite, EUO (e.g., EU-1 or ZSM-50), FAU, GIS (e.g. , Zeolite P), MTW (e.g., ZSM-12), MFI (e.g., ZSM-5), FER (e.g., Ferrierite), MOR (e.g., Mordenite), SOD (e.g., Sodalite), SFE (e.g., EMM-74) and / or ANA (e.g., Analcine). The *MRE 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-*MRE” framework type), 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).

[0050] The *MRE 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 noncrystalline form).

[0051] The molecular sieve obtainable by (or obtained by) the method 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 third 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 *MRE framework type, e.g., ZSM-48, obtainable by (or obtained by) the method of the present disclosure, in a hydrocarbon chemical conversion process.

[0052] The molecular sieve materials 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 more desired 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.

[0053] 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 effectivelycatalyzed 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, such as isomerization of olefins or of aromatic compounds, 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.

[0054] 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.

[0055] 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 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 the amount 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.

[0056] 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.

[0057] 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.

[0058] 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 nr / g.

[0059] 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 the range of about 2 to about 95, optionally from about 20 to about 90 weight percent of the composite.

[0060] 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 IIIAelement, 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.

[0061] 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

[0062] The present invention is further illustrated below without limiting the scope thereto.

[0063] In these examples, the X-ray diffraction (XRD) patterns of the as-synthesized and calcined materials were recorded on a Bruker D8 Endeavor Automated X-Ray Powder Diffractomer 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, I / L, is 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, Flo, where lois 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 relative intensities, 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.

[0064] The scanning electron microscopy (SEM) images of the as-synthesized materials were obtained on a Hitachi S4800 Field Emission 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 crystallinematerials. 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 product XRD patterns.

[0065] The following measurements were conducted on samples that were ion-exchanged (when M was present) and calcined. For each sample subjected to ion-exchange and calcination, the procedure used was as follows: the as-prepared sample was washed two times with a IM ammonium nitrate solution and then calcined at 500°C for 16 hours.

[0066] The overall BET surface area (Sppy) of the materials was determined by the BET method as described by S. Brunauer, P.H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309, incorporated herein by reference, using nitrogen adsorption-desorption at liquid nitrogen temperature. The external surface area (SexL) of the material was obtained from the t-plot method, and the micropore surface area (Smjcro) of the material was calculated by subtracting the external surface area (Sexl) from the overall BET surface area (Sggy ).

[0067] The micropore volume (Vm[cro) and total pore volume (Vlol) of the materials can be determined using methods known in the relevant art. For example, the micropore and total pore volumes of the materials can be measured with nitrogen physisorption, and the data can be analyzed by the t-plot method described in Lippens, B.C. et al., “Studies on pore system in catalysts: V. The t method”, J. Catal., 4, 319 (1965), which describes micropore and total pore volume methods and is incorporated herein by reference.

[0068] The molar ratios and conditions used for the syntheses of Examples 2 to 20, as well as the resulting products, are detailed below and summarized in Figures 7 and 8. Figure 7 contains the molar ratios, conditions, and resulting products for Examples 2-12. Figure 8 contains the molar ratios, conditions, and resulting products for Examples 13-20.Synthesis of l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation (SDA)

[0069] l,2-dimethylimidazo[l,2-a]pyridin-l-ium iodide: A mixture of 26.52 g (200.65 mmol) of 2-methylimidazo[l,2-a]pyridine and 29.90 g (210.68 mmol) of methyl iodide in 250 mL of acetonitrile was stirred at room temperature for 16 hours. The solids werefiltered and rinsed with 200 mL of ethyl acetate and allowed to air dry for 30 minutes prior to taking an I H-NMR. The 1 H-NMR confirmed the clean desired product had been obtained.

[0070] l,2-dimethylimidazo[l,2-a]pyridin-l-ium hydroxide: The iodide salt was ion- exchanged with ion-exchange resin Amberlite® IRN78 OH hydroxide form (with iodide: resin: water ratio of 1 : 3.5 : 5) to the hydroxide form. The exchange was performed at room temperature overnight.Synthesis of *MRE molecular sieve (Si / Al 50)

[0071] In a PTFE liner for a 10 mL Steel Parr autoclave, the following were mixed: 2.2 g of SDA solution (8.2 wt%), 0.74 g of NaOH solution (4 wt%), 0.014 g of Al(0H)3 (Sigma, 54 wt% AI2O3), 1.23 g of deionized water, 6 mg of ZSM-48 seed, and 0.44 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:20 H2O : 1 SiO2: 0.01 AI2O3 : 0.15 QOH : 0.1 NaOH

[0072] 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 1 week 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.

[0073] XRD analysis of the as-synthesized and calcined materials, as illustrated in Figures 1 and 2, showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.

[0074] Figure 3 is a SEM image of the as-synthesized material of Example 2, indicating that the zeolite has a uniform rod-like morphology with a particle diffusion length of about 1 -2 pm.

[0075] The calcined sample had a micropore surface area of 228 m2 / g, an external surface area of 45 m2 / g, and a micropore volume of 0.08 cm / g.Synthesis of *MRE molecular sieve (Si / Al =38.5)

[0076] Example 3 was conducted in similar conditions as Example 2, except for the use of0.0182 g of Al(0H)3 (Sigma, 54 wt% AI2O3), to produce a synthesis mixture having the following composition in terms of molar ratios:20 H2O : 1 SiO2: 0.013 AI2O3 : 0.15 QOH : 0.1 NaOH

[0077] After 1 week at 160°C, XRD analysis of the as-synthesized material, as illustrated in Figure 4, showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.

[0078] After calcination to 600°C in the same conditions as Example 2, the calcined sample had a micropore surface area of 212 m2 / g, an external surface area of 45 m2 / g, and a micropore volume of 0.08 cm3 / g. The powder XRD pattern of the calcined sample is shown in Figure 5. Example 4: Synthesis of *MRE molecular sieve (Si / Al=40)

[0079] In a PTFE liner for a 10 mL Steel Parr autoclave, the following were mixed: 3.28 g of SDA solution (8.2 wt%), 0.43 g of NaOH solution (10 wt%), 2.4 g of deionized water, 0.68 g of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 40 (available from Zeolyst as CBV780), and 7 mg of ZSM-48 seed to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.0125 A12O3: 0.15 QOH : 0.1 NaOH

[0080] 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 4 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried. XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Example 5: Synthesis of *MRE molecular sieve (Si / Al= 50)

[0081] Example 5 was conducted in similar conditions as Example 2, except for the use of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 50 (available from Tosoh as HUA385) as the source of Si and Al and the use of a lower amount of NaOH, to produce a synthesis mixture having the following composition in terms of molar ratios:20 H2O : 1 SiO2: 0.01 A12O3: 0.15 QOH : 0.05 NaOH

[0082] After 9 days at 160°C, XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Example 6: Synthesis of *MRE molecular sieve (Si / AU 30)

[0083] Example 6 was conducted in the same conditions as Example 5, except for the use of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 30 (available from Zeolyst as CBV360) as the source of Si and Al, to produce a synthesis mixture having the following composition in terms of molar ratios:20 H2O : 1 SiO2: 0.0167 A12O3: 0.15 QOH : 0.05 NaOH

[0084] After 9 days at 160°C, XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Synthesis of *MRE molecular sieve (Si / Al 50)

[0085] Example 7 was conducted in similar conditions as Example 5, except for the use of a higher amount of water and the use of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 30 (available from Zeolyst as CBV360) in combination with Ludox HS40 (40 wt% colloidal silica suspension) and sodium aluminate (Na A IO, 23.5 wt% solution) as the sources of Si and Al, to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.01 A12O3: 0.15 QOH : 0.05 NaOH

[0086] After 10 days at 160°C, XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Synthesis of *MRE molecular sieve (Si / Al 125)

[0087] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed: 3.1 g of SDA solution (8.2 wt%), 0.62 g of NaOH solution (10 wt%), 0.01 g of A1(OH)3(Sigma, 54 wt% A12O3), 1.59 g of deionized water, 30 mg of ZSM-48 seed, 1.54 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:12.8 H2O : 1 SiO2: 0.004 A12O3: 0.06 QOH : 0.06 NaOH

[0088] 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 1 week under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried. XRD analysis of the as-synthesized material showed the material to have a powderXRD pattern of ZSM-48 or *MRE framework type.Synthesis of *MRE molecular sieve (Si / Al 166)

[0089] Example 9 was conducted in similar conditions as Example 8, except for the use of precipitated silica (Sipemat® 340 available from Evonik) as the Si source and A1(OH)3(Sigma,54 wt% A12O3) as the Al source, to produce a synthesis mixture having the following composition in terms of molar ratios:12.8 H2O : 1 SiO2: 0.003 A12O3: 0.06 QOH : 0.06 NaOH

[0090] After 7 days at 160°C, XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Synthesis of *MRE molecular sieve (Si / Al 50, no seeds)

[0091] Example 10 was conducted in the same conditions and molar ratios as Example 7, except for the absence of seeds and the use of Beta zeolite having a Si / Al molar ratio of 19 (available from Zeolyst as CP 814C) in combination with Ludox HS40 (40 wt% colloidal silica suspension) and sodium aluminate (NaAlOr, 23.5 wt% solution) as the sources of Si and Al, to produce a synthesis mixture having the following composition in terms of molar ratios:30 H2O : 1 SiO2: 0.01 A12O3: 0.15 QOH : 0.05 NaOH

[0092] After 3 weeks at 160°C, XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.11 to 14: Synthesis of *MRE molecular sieve (Si / Af 30, 40, 50, 250, no seeds)

[0093] Examples 11 to 14 further exemplify the synthesis of *MRE molecular sieves in the absence of seeds at different Si / Al molar ratios. The detailed conditions are available in Figures7 and 8. XRD analysis of the as-synthesized materials of Examples 1 1 to 14 showed the materials to have powder XRD patterns of ZSM-48 or *MRE framework type.Synthesis of *MRE molecular sieve in the presence of HMCh (Si / Af 40)

[0094] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed: 2.1 g of SDA solution (8.2 wt%), 1.31 g of hexamethonium dichloride (HMCh, 56%wt) as additional or second structure directing agent, 1 g of NaOH solution (10 wt%), 0.13 g sodium aluminate (NaA102, 23.5 wt% solution), 1.75 g of deionized water, and 1.44 g of precipitated silica (Sipernat® 340 available from Evonik) and 1-2 wt% ZSM-48 seed to produce a synthesis mixture having the following composition in terms of molar ratios:15 H2O : 1 SiO2: 0.0124 A12O3: 0.05 QOH : 0.02 HMC12: 0.14 NaOH

[0095] 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 3 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried.

[0096] XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type. Figure 6 is a SEM image of the as- synthesized material of Example 15, indicating that the zeolite has a uniform particle size of about 50 nm.Synthesis of *MRE molecular sieve in the presence of HMCh (Si / AL 40)

[0097] Example 16 was conducted in the same conditions as Example 15, except for the use of Ultrastable Y (USY) zeolite with a Si / Al molar ratio of 250 (available from Tosoh asHUA390) in combination with sodium aluminate solution (NaA102, 23.5 wt%) as the Si andAl sources, to produce a synthesis mixture having the following composition in terms of molar ratios:15 H2O : 1 SiO2: 0.0124 A12O3: 0.05 QOH : 0.02 HMC12: 0.14 NaOH

[0098] After 3 days at 160°C, XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Examples 17-18: Synthesis of *MRE molecular sieve in the presence of HMC12(Si / Al= 40)

[0099] Examples 17 and 18 were conducted in similar conditions as Example 16, except for lower amounts of SDA (QOH / Si of 0.025 and 0.01 respectively).

[0100] After 3 days at 160°C, XRD analysis of the as-synthesized materials of Examples 17 and 18 showed the materials to have a powder XRD pattern of ZSM-48 or *MRE framework type.Example 19: Synthesis of *MRE molecular sieve in the presence of PMBr2(Si / Al= 50)

[0101] In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed: 2 g of SDA solution (8.2 wt%), 1.04 g of pentamethonium dibromide (PMBr2, 20%wt) as additional or second structure directing agent, 1.21 g of NaOH solution (10 wt%), 0.086 g of sodium aluminate (NaA102, 23.5 wt% solution), 3.12 g of deionized water, and 1.2 g of precipitated silica (Sipernat® 340 available from Evonik) and 1-2 wt% ZSM-48 seed to produce a synthesis mixture having the following composition in terms of molar ratios:20 H2O : 1 SiO2: 0.01 A12O3: 0.05 QOH : 0.03 PMBr2: 0.18 NaOH

[0102] 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 3 days under tumbling conditions (about 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried.

[0103] XRD analysis of the as-synthesized material of Example 19 showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.Example 20: Synthesis of silicate *MRE molecular sieve in fluoride media (no seeds)

[0104] 1.06 g of tetraethylorthosilicate (TEOS, >99 wt%) was hydrolyzed at room temperature in 7.1 g of SDA (5.9%wt) for about 2-3 hours. The mixture was then heated at about 50°C to remove the ethanol and water. 0. 11 g of HF (48 wt% solution) were added to the mixture to produce a synthesis mixture having the following composition in terms of molar ratios:12 H20: 1 SiO2: 0.5 QOH : 0.5 HF

[0105] The resulting thick paste was homogenized by hand in a Teflon® containing and transferred to a 10 mL Teflon-lined stainless-steel autoclave (Parr). The autoclave was heated at 160°C for 9 days in a tumbling oven (about 40 rpm). After 9 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.

[0106] XRD analysis of the as-synthesized material showed the material to have a powder XRD pattern of ZSM-48 or *MRE framework type.

[0107] 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.

[0108] 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.

[0109] Additionally or alternately, the invention relates to:

[0110] Embodiment 1 : A method of making a molecular sieve of *MRE framework type, comprising the steps of (a) preparing a synthesis mixture comprising water, at least one source of silica, optionally at least one source of alumina, a structure directing agent (Q) comprising at least one l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation, a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), and optionally a source of fluoride ions (F), wherein the synthesis mixture comprises Si and Al in a Si / Al molar ratio of at least 30; (b) heating said synthesis mixture under crystallization conditions including atemperature 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).

[0111] Embodiment 2: The method of embodiment 1, further comprising treating the molecular sieve recovered in step (c) to remove at least part of the structure directing agent (Q).

[0112] Embodiment 3: The method of embodiment 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.

[0113] Embodiment 4: 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 rangeSi / Al 30 - oo 30 - 500 (if Al present) 30 - 300 (if Al present)Q / Si 0.01 - 1.0 0.025 - 0.8 0.05 - 0.6OH / Si 0.01 - 1.5 0.05 - 1.0 0.1 - 0.8F / Si 0 - 1.0 0.1 - 0.8 (if F present) 0.2 - 0.7 (if F present)M / Si 0 - 1.0 0.01 - 0.5 (if M present) 0.05 - 0.3 (if M present)H2O / Si 1 - 100 5 - 80 10 - 50

[0114] Embodiment 5: The method of any one of the preceding embodiments, wherein the synthesis mixture further comprises a second structure directing agent (Q’) selected from structure directing agents traditionally used for the synthesis of molecular sieves of *MRE framework type, in particular a second structure directing agent (Q’) selected from the group consisting of pentamethonium cation ((CH3)3N+(CH2)sN+(CH3)3), “Mee-diquat-5 cation”), hexamethonium cation ((CH3)3N+(CH2)eN+(CH3)3), “Mee-diquat-6 cation”), and mixtures thereof.

[0115] Embodiment 6: The method of embodiment 5, wherein the synthesis mixture comprises the second structure directing agent (Q’) in a Q7Si molar ratio of from 0.01 to 0.5, preferably from 0.01 to 0.25, more preferably from 0.01 to 0.1, most preferably from 0.01 to 0.05 or from 0.01 to 0.03.

[0116] Embodiment 7: The method of embodiment 5 or 6, wherein the synthesis mixture comprises the structure directing agent (Q) in a Q / Si molar ratio of from 0.01 to 0.5, preferably from 0.01 to 0.1, more preferably from 0.01 to 0.05.

[0117] Embodiment 8: The method of any one of the preceding embodiments, wherein the synthesis mixture comprises seeds, in particular seeds of *MRE, FAU and / or BEA framework type.

[0118] Embodiment 9: The method of any one of the preceding embodiments, wherein the molecular sieve of *MRE framework type is selected from the group consisting of COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, RUB-58, ZSM-48, and mixtures thereof, preferably wherein the molecular sieve of *MRE framework type is ZSM-48.

[0119] Embodiment 10: A molecular sieve of *MRE framework type obtainable by the method of any one of the preceding embodiments.

[0120] Embodiment 11: A process of converting an organic compound to a conversion product, which comprises contacting the organic compound with the molecular sieve of *MRE framework type of embodiment 10.

Claims

CLAIMS1. A method of making a molecular sieve of *MRE framework type, comprising the following steps: (a) preparing a synthesis mixture comprising water, at least one source of silica, optionally at least one source of alumina, a structure directing agent (Q) comprising at least one l,2-dimethylimidazo[l,2-a]pyridin-l-ium cation, a source of hydroxide ions (OH), optionally a source of alkali and / or alkaline earth metal element (M), and optionally a source of fluoride ions (F) ^wherein the synthesis mixture comprises Si and Al in a Si / Al molar ratio of at least 30; (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) is in the form of a halide, hydroxide or nitrate, preferably wherein the structure directing agent (Q) is in its hydroxide form.

3. The method of claim 1 or 2, wherein the synthesis mixture has the following composition in terms of molar ratios:Molar ratios Typical range Preferred range More preferred rangeSi / Al 3 ,n0 - co 30 - 500 (if Al present) 30 - 300 (if Al present)Q / S10.01 - 1.0 0.025 - 0.8 0.05 - 0.60H / S10.01 - 1.5 0.05 - 1.0 0.1 - 0.8F / S10 - 1.0 0.1 - 0.8 (if F present) 0.2 - 0.7 (if F present)M / S10 - 1.0 0.01 - 0.5 (if M present) 0.05 - 0.3 (if M present)H2O / St 1 - 100 5 - 80 10 - 504. The method of any one of the preceding claims, wherein the synthesis mixture further comprises a second structure directing agent (Q’) selected from structure directing agents traditionally used for the synthesis of molecular sieves of *MRE framework type, in particular a second structure directing agent (Q’) selected from the group consisting of pentamethonium cation ((CH3)3N+(CH2)sN+(CH3)3), “Me&-diquat-5 cation”), hexamethonium cation ((CH3)3N+(CH2)eN+(CH3)3), “Mee-diquat-6 cation”), and mixtures thereof.

5. The method of claim 4, wherein the synthesis mixture comprises the second structure directing agent (Q’) in a Q7Si molar ratio of from 0.01 to 0.5, preferably from 0.01 to 0.25, more preferably from 0.01 to 0.1, most preferably from 0.01 to 0.05 or from 0.01 to 0.03.

6. The method of claim 4 or 5, wherein the synthesis mixture comprises the structure directing agent (Q) in a Q / Si molar ratio of from 0.01 to 0.5, preferably from 0.01 to 0.1, more preferably from 0.01 to 0.05.

7. The method of any one of the preceding claims, wherein the synthesis mixture comprises seeds, in particular seeds of *MRE, FAU and / or BEA framework type.

8. The method of any one of the preceding claims, wherein the molecular sieve of *MRE framework type is selected from the group consisting of COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, RUB-58, ZSM-48, and mixtures thereof, preferably wherein the molecular sieve of *MRE framework type is ZSM-48.

9. A molecular sieve of *MRE framework type obtainable by the method of any one of the preceding claims.

10. A process of converting an organic compound to a conversion product, which comprises contacting the organic compound with the molecular sieve of *MRE framework type of claim 9.

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