KR20240134905A - EMM-70 Zeolite Composition, Synthesis and Uses - Google Patents

Abstract

The present disclosure relates to a zeolite designated EMM-70 characterized by a unique powder XRD pattern, a process for its preparation and uses thereof.

Description

EMM-70 Zeolite Composition, Synthesis and Uses

Cross-reference to related applications

This application claims priority to and the benefit of U.S. Provisional Application No. 63/301705, filed January 21, 2022, the entire contents of which are incorporated herein by reference.

Technical field

The present disclosure relates to a zeolite composition, a method for producing the same, and uses thereof.

Both natural and synthetic molecular sieve materials can be used as adsorbents and can have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AlPO, and mesoporous materials, are ordered porous crystalline materials having a definite crystal structure as determined by X-ray diffraction (XRD). Certain molecular sieves are ordered and produce unique, identifiable XRD patterns. Within a particular molecular sieve material, there may be numerous cavities that may be interconnected by a number of channels or pores. These cavities and pores are uniform in size within a particular molecular sieve material. The dimensions of these pores are such that, for example, molecules of a certain size are adsorbed while molecules of a larger size are rejected, and thus such materials have come to be known as "molecular sieves" and are used in a variety of industrial processes, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

Molecular sieves used in catalysis and adsorption include any of the naturally occurring or synthetic crystalline molecular sieves. Examples of such molecular sieves include large pore zeolites, medium pore zeolites, and small pore zeolites. These zeolites and their isotypes are classified by the Structure Committee of the International Zeolite Association according to the rules of the IUPAC Zeolite Nomenclature Commission. According to this classification, framework type zeolites and other crystalline microporous molecular sieves whose structures have been established are assigned three-letter codes, which are described in the literature [Baerlocher, L. et al. (2007) "Atlas of Zeolite Framework Types", eds. Elsevier , Sixth Edition] (incorporated herein by reference). These zeolites and their isotypes are also described at https://america.iza-structure.org/IZA-SC/ftc_table.php . Large pore zeolites typically have pore sizes greater than about 7 Å and include, for example, LTL, VFI ("extra-large" 18R), MAZ, FAU, OFF, *BEA, and MOR framework type zeolites. Examples of large pore zeolites include mazite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and beta. Intermediate pore size zeolites typically have pore sizes from about 5 Å to less than about 7 Å and include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites. Examples of intermediate pore size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite-1, and silicalite-2. Small pore size zeolites have pore sizes of less than about 3 Å to about 5.0 Å and include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework type zeolites. Examples of small pore zeolites include ZK-4, SAP0-34, SAP0-35, ZK-14, SAP0-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, and ALPO-17.

The idealized inorganic framework structure of a zeolite is a silicate framework in which every tetrahedral atom is linked to the four nearest tetrahedral atoms next to it by oxygen atoms. The term "silicate" as used herein means a material containing at least silicon and oxygen atoms (i.e., -O-Si-O-Si-) bonded alternately to each other, and optionally including other atoms within the inorganic framework structure, such as boron, aluminum, or other metals, such as transition metals such as titanium, vanadium, or zinc. Atoms other than silicon and oxygen within the framework silicate occupy some of the lattice sites that would be occupied by the silicon atoms of an "all-silica" framework silicate. Therefore, the term "skeletal silicate" as used herein means an atomic lattice comprising any of a silicate, a borosilicate, a gallosilicate, a ferrisilicate, an aluminosilicate, a titanosilicate, a zinkosilicate, a vanadosilicate, and the like.

The structure of the framework silicate within a given zeolite determines the size of the pores or channels present within it. The pore or channel size can determine the types of processes for which a given zeolite is applicable. Currently, over 200 unique zeolite framework silicate structures are known and recognized by the Structure Committee of the International Zeolite Association, defining a variety of pore shapes and orientations.

The framework silicate of a zeolite is generally characterized by its ring size, which represents the number of silicon atoms (or alternative atoms as listed above) that are tetrahedrally coordinated with oxygen atoms within the loop to define a void or channel within the zeolite. For example, an "eight-ring" zeolite is a zeolite having voids or channels defined by eight alternating tetrahedral atoms and eight oxygen atoms within the loop. The voids or channels defined within a given zeolite may be symmetrical or asymmetrical, depending on various structural constraints present in the particular framework silicate.

The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthesis mixture that includes a source of all the elements present in the zeolite, such as a source of silica as well as a source of alumina. In many cases, a structure directing agent (SDA) is also present. A structure directing agent is a compound that is believed to promote the formation of the molecular sieve and acts as a template upon which a specific molecular sieve structure can be formed, thereby promoting the formation of the desired molecular sieve. A variety of compounds have been used as structure directing agents, including various types of quaternary ammonium cations. Typically, zeolite crystals are formed around the structure directing agent, and upon completion of crystallization, the structure directing agent occupies the pores of the zeolite. Thus, since the "as-synthesized" zeolite contains the structure directing agent in its pores, after crystallization the "as-synthesized" zeolite is typically subjected to a treatment step, such as a calcination step, to remove the structure directing agent.

For example, WO 2004/013042 A1 discloses the preparation of SSZ-64 molecular sieves made using structural derivatives having an N-cyclobutylmethyl-N-ethylhexamethyleneiminium cation or an N-cyclobutylmethyl-N-ethylheptamethyleneiminium cation.

Although many different zeolites have been discovered, there is a continuing need for new zeolites with desirable properties for gas separation and drying, organic conversion reactions, and other applications. New zeolites may provide improved selectivity in these processes by including novel internal pore structures. It is also important to find new structure-directing agents and more efficient molecular sieve synthesis methods to facilitate the preparation of new molecular sieves and/or reduce the cost of preparing already known zeolites.

The present disclosure relates to zeolite, a method for producing the same, and uses thereof.

In a first embodiment, the present disclosure relates to a zeolite having an X-ray diffraction pattern comprising 2-theta (°) peaks shown in Table 1, in calcined form (e.g., where at least a portion of the SDA has been removed).

[Table 1]

In a second embodiment, the present disclosure relates to a zeolite having an X-ray diffraction pattern comprising 2-theta (°) peaks shown in Table 2, in an as-synthesized form (e.g., where SDA is not removed).

[Table 2]

In a third embodiment, the present disclosure relates to a method for preparing a zeolite, particularly a zeolite of the first or second embodiment, comprising the steps of: (a) preparing a synthetic mixture comprising water, a source of an oxide of a tetravalent element (Y), a source of an oxide of a trivalent element (X), a structure directing agent (Q), optionally a source of hydroxide ions (OH), optionally a source of an alkali and/or alkaline earth metal element (M), and optionally a source of fluoride (F),

The above structural inducer (Q) comprises at least one cation selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following chemical formula I:

(chemical formula I)

[In the above formula, R is methyl or ethyl];

wherein the synthetic mixture has a Y/X molar ratio of less than 30, and if a fluoride (F) source is present, a F/Y molar ratio of less than 0.05;

(b) heating the synthetic mixture under crystallization conditions including a temperature of 100 to 200° C. for a time sufficient to form crystals of the zeolite;

(c) recovering at least a portion of the zeolite from step (b); and

(d) optionally, a step of treating the zeolite recovered in step (c) to remove at least a portion of the structure-directing agent (Q).

In a fourth embodiment, the present disclosure relates to a method of converting an organic compound into a conversion product, comprising the step of contacting the organic compound with a zeolite prepared according to the first or second embodiment or according to the method of the third embodiment.

These and other features and properties of the present invention and their advantageous applications and/or uses will become apparent from the following detailed description. Of course, it will be appreciated that features described in connection with 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 herein, including the “Summary of the Invention” section above, may be combined to form a combination of features not specifically described herein.

Figure 1 shows a SEM image of the synthesized product of Example 2.
Figure 2 shows a powder XRD pattern of the synthesized product of Example 5.
Figure 3 shows a powder XRD pattern of the calcined product of Example 5.
Figure 4 shows a SEM image of the synthesized product of Example 5.

The present disclosure relates to a zeolite composition, a process for preparing the same, and uses thereof. The zeolite may be referred to as EMM-70 zeolite or EMM-70 material.

In a first embodiment, the present disclosure relates to a zeolite having an X-ray diffraction pattern comprising 2-theta (°) peaks shown in Table 1, in calcined form (e.g., where at least a portion of the SDA has been removed).

[Table 1]

In a further embodiment, the zeolite in calcined form can have an X-ray diffraction pattern comprising peaks at 2-theta (°) as shown in Table 1A, wherein the d-spacing values have a deviation determined based on a corresponding deviation of ±0.20 2-theta (°) when converted to the corresponding value for d-spacing using Bragg's law.

[Table 1A]

The XRD pattern having the XRD peaks described herein uses Cu( _Kα ) radiation.

In one or more additional embodiments, the zeolite in calcined form can have a micropore volume of from 0.05 to 0.3 cc/g, or from 0.1 to 0.25 cc/g, for example, 0.18 cc/g.

In one or more further embodiments, the zeolite in calcined form can have a micropore surface area of from 100 to 800 m ² /g, or from 300 to 600 m ^{2 /} g, for example 505 m ² /g, and/or an external surface area of from 5 to 200 m ² /g, or from 20 to 100 m ² /g, for example 63 m ² /g.

In one or more additional embodiments, the zeolite in calcined form may optionally be represented by the molecular formula of Formula II:

(m)X ₂ O ₃ : YO ₂ (chemical formula II)

In the above formula, 0.017≤m≤0.1, X is a trivalent element, and Y is a tetravalent element. Y may include one or more of Si and Ge. For example, Y may include Si or be Si. X may include one or more of Al and B. For example, X may include Al and/or B or may be Al and/or B, and in particular, X may include Al or be Al. In the formula II, the oxygen atom may be replaced by a carbon atom (e.g., in the form of CH ₂ ), which may be derived from the source of the component used to prepare the zeolite in the as-prepared state. The oxygen atom in the formula II may be replaced by a nitrogen atom, for example, after the SDA is removed. The formula II may represent a typical zeolite framework as defined in the present disclosure in its calcined form, and is not meant to be the only representation of the zeolite. In calcined form, the zeolite may contain SDA and/or impurities after appropriate treatment to remove the SDA and impurities, which are not considered in Formula II. Furthermore, Formula II does not include protons and charge compensating ions that may be present in the zeolite in the calcined state.

The variable m represents the molar ratio relationship of X ₂ O ₃ to YO ₂ in Chemical Formula II. For example, when m is 0.025, the molar ratio of YO ₂ to X ₂ O ₃ is 40, and the molar ratio of Y to X is 20 (e.g., the molar ratio of Si/Al is 20). m can vary from 0.017 to 0.1, for example, at least 0.017, or at least 0.020, or at least 0.025 and up to at most 0.1, or at most 0.05, for example, 0.033. The molar ratio of Y to X can be from 1 to less than 30, such as at least 5, or at least 10, and at most 29, or at most 25, or at most 20, for example, 15.

In a second embodiment, the present disclosure relates to a zeolite having an X-ray diffraction pattern comprising peaks at 2-theta (°) as shown in Table 2, in a synthesized form (e.g., where SDA is not removed), particularly a zeolite as defined in the first embodiment.

[Table 2]

In a further embodiment, the synthesized form of the zeolite can have an X-ray diffraction pattern comprising 2-theta (°) peaks as shown in Table 2A, wherein the d-spacing values have a deviation determined based on a corresponding deviation of ±0.20 2-theta (°) when converted to the corresponding value for d-spacing using Bragg's law.

[Table 2A]

The XRD pattern having the XRD peaks described herein uses Cu( _Kα ) radiation.

In one or more additional embodiments, the synthetic form of said zeolite may optionally be represented by the molecular formula of Formula III:

(q)Q : (m)X ₂ O ₃ : YO ₂ (chemical formula III)

In the above formula, 0 ≤ q ≤ 0.5, 0.017 ≤ m ≤ 0.1, and Q comprises at least one cation selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following chemical formula I:

(chemical formula I)

(wherein R is methyl or ethyl); X is a trivalent element as defined for formula II, and Y is a tetravalent element as defined for formula II. Formula III contains a structure directing agent (Q) as it may represent the framework of a typical zeolite as defined in the present disclosure in its synthesized form, but is not meant to be the only representation of such a material. The synthesized form of the zeolite may contain impurities not contemplated by formula III. Furthermore, formula III does not include protons and charge compensating ions which may be present in the synthesized form of the zeolite.

The variable m represents the molar ratio relationship of X ₂ O ₃ to YO ₂ in Formula III. The values of the variable m in Formula III are the same as described herein for Formula II.

The variable n represents the molar relationship of Q to YO ₂ in chemical formula III. For example, when n is 0.1, the molar ratio of Q to YO ₂ is 0.1. The molar ratio of Q to YO ₂ can be from 0 to 0.5, for example, from 0.02 to 0.4, for example, from 0.05 to 0.3.

In a third embodiment, the present disclosure relates to a process for preparing a zeolite, particularly a zeolite as defined in the first or second embodiment, for example EMM-70, comprising the following steps:

(a) a step of preparing a synthetic mixture comprising water, a source of a tetravalent element (Y) oxide, a source of a trivalent element (X) oxide, a structure-directing agent (Q), optionally a source of hydroxide ions (OH), and optionally a source of an alkali and/or alkaline earth metal element (M),

The above structural inducer (Q) comprises at least one cation selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following chemical formula I:

(chemical formula I)

(in the above formula, R is methyl or ethyl),

wherein the synthetic mixture has a Y/X molar ratio of less than 30, and if a fluoride (F) source is present, the F/Y molar ratio is less than 0.05;

(b) heating the synthetic mixture under crystallization conditions including a temperature of 100 to 200° C. for a time sufficient to form crystals of the zeolite;

(c) recovering at least a portion of the zeolite from step (b); and

(d) optionally, a step of treating the zeolite recovered in step (c) to remove at least a portion of the structure-directing agent (Q).

The structure directing agent (Q) comprises at least one cation selected from the group consisting of 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, 2-ethyl-1,3-dimethyl-4,5,6,7-tetrahydrobenzimidazolium cation and mixtures thereof. The structure directing agent (Q) can be present in any suitable form, for example a halide, such as a fluoride, chloride, iodide or bromide, a hydroxide or a nitrate, for example in the form of a hydroxide. The structure-inducing agent (Q) can be present in the synthesis mixture in a Q/Y molar ratio of from 0.05 to 1.0, for example, from 0.1 or more, from 0.15 or more, from 0.2 or more, to 0.8 or less, from 0.7 or less, or from 0.6 or less, for example, from 0.1 to 0.8, or from 0.15 to 0.5, for example, from 0.2 to 0.4.

The synthesis mixture comprises one or more sources of an oxide of the tetravalent element Y, such as Si and/or Ge, preferably Y comprises Si, more preferably Y is Si. Suitable sources of the tetravalent element Y that can be used to prepare the synthesis mixture depend on the element Y selected. In embodiments where Y is silicon, suitable Si sources (e.g., silicon oxide sources) for use in the process include silicates, such as tetraalkyl orthosilicates, such as tetramethylorthosilicate (TMOS) and tetraethylorthosilicate (TEOS); fumed silicas, such as Aerosil® (available from Evonik), Cabosperse® (available from Cabot), and Cabosil® (available from DMS); precipitated silicas, such as Ultrasil® and Sipemat® 340 (available from Evonik); alkali metal silicates, such as potassium silicate and sodium silicate, and silicates, such as those available from E.I. An aqueous colloidal suspension of silica sold under the trade name Ludox® by du Pont de Nemours or under the trade name Aerodisp® by Evonik; preferably silicates, fumed silica, precipitated silica, alkali metal silicates, colloidal silica. In embodiments where Y is germanium, suitable Ge sources include germanium oxide.

The composite mixture comprises one or more sources of an oxide of a trivalent element X, such as Al and/or B, wherein preferably X comprises Al and/or B, for example Al, and more preferably X is Al and/or B, for example Al. Suitable sources of the trivalent element X that can be used to prepare the composite mixture vary depending on the element X selected. In embodiments where X is aluminum, suitable Al sources (e.g., aluminum oxide sources) for use in the process include aluminum salts, such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, especially the water-soluble salts, alkali metal aluminates, such as sodium aluminate, and aluminum alkoxides, such as aluminum isopropoxide, as well as hydrated aluminum oxides, such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other sources of aluminum include, but are not limited to, other soluble aluminum salts, aluminum alkoxides such as sodium aluminate, aluminum isopropoxide, or aluminum metal such as aluminum in chip form. Particularly suitable sources of alumina are soluble salts such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, and alkali metal aluminates such as sodium aluminate and potassium aluminate. In embodiments where X is boron, suitable sources of B include boric acid and borates such as sodium tetraborate or borax and potassium tetraborate. Boron sources tend to be more soluble in hydroxide-mediated synthesis systems than aluminum sources.

Alternatively or in addition to the previously mentioned Y and X sources, sources containing both Y and X elements, such as Si and Al sources, may also be used. Examples of suitable sources containing both Si and Al elements include amorphous silica-alumina gels or dried silica alumina powders, silica alumina, clays (e.g., kaolin, metakaolin), and zeolites, particularly aluminosilicates, such as synthetic faujasites and ultrastable faujasites, e.g., Ultrastable Y (USY), beta or other large to medium pore zeolites.

The synthetic mixture can have a Y/X molar ratio of from 1 to less than 30, for example from 5 to 25, for example from 5 or from 10 to 20, for example 15.

In a preferred embodiment, Y is Si, X is Al, and the zeolite is an aluminosilicate. In another preferred embodiment, Y is Si, X is B, and the zeolite is a borosilicate.

The synthetic mixture may optionally comprise one or more sources of alkali or alkaline earth metal cations (M). M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, calcium, magnesium and mixtures thereof, preferably sodium and/or potassium, more preferably sodium. The sodium source, if present, may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate or a sodium salt such as NaCl, NaBr or sodium nitrate. The potassium source, if present, may be a potassium salt such as potassium hydroxide, potassium aluminate, potassium silicate, KCl or KBr or potassium nitrate. The lithium source, if present, may be lithium hydroxide or a lithium salt such as LiCl, LiBr, LiI, lithium nitrate or lithium sulfate. The rubidium source, if present, may be rubidium hydroxide or a rubidium salt such as RbCl, RbBr, RBI or rubidium nitrate. The calcium source, if present, can be, for example, calcium hydroxide. The magnesium source, if present, can be, for example, magnesium hydroxide. An alkali or alkaline earth metal cation M may also be present in one or more sources of a trivalent element X, such as sodium aluminate, sodium tetraborate, potassium tetraborate, and/or one or more sources of a tetravalent element Y, such as potassium silicate and/or sodium silicate. The synthesis mixture can include the alkali or alkaline earth metal cation (M) source in an M/Y molar ratio of from 0 to 1.0, for example from 0.05 to 0.5, for example from 0.05 to less than 0.1. Alternatively, the synthesis mixture can be substantially free of alkali or alkaline earth metal cation (M).

The synthetic mixture may also optionally contain one or more sources of hydroxide ions (OH). For example, the hydroxide ions may be present as a counter ion of the structure directing agent (Q) or by using aluminum hydroxide as a source of Al. Suitable sources of hydroxide ions may also be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide and mixtures thereof; for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium 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 synthetic mixture can comprise a hydroxide ion source in an OH/Y molar ratio of from 0 to 1.0, for example from 0.05 to 0.8, for example from 0.1 to 0.6 or from 0.15 to 0.5, for example from 0.2 to 0.5. Alternatively, the synthetic mixture can be substantially free of a hydroxide ion source.

The synthesis mixture used in the preparation of the EMM-70 material comprises fluoride ions (F) in a F/Si molar ratio of less than 0.05, for example, from 0 to 0.04, or from 0 to 0.02, or from 0 to 0.01, for example, 0. In particular, the synthesis mixture used in the preparation of the EMM-70 zeolite is substantially free of fluoride ions (F). This means that no source of fluoride ions is added to the synthesis mixture in any substantial amount, for example, the synthesis mixture has a F/Si molar ratio of less than 0.05, for example, less than 0.02, less than 0.01 or even less than 0.005, for example, 0. The fluoride ions (F), if present, are any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture, for example, hydrogen fluoride (HF); Preferably a salt containing one or more fluoride ions, such as a metal fluoride wherein the metal is sodium, potassium, calcium, magnesium, strontium or barium; ammonium fluoride (NH ₄ F); and ammonium difluoride (NH ₄ HF ₂ ). For example, a small amount of fluoride ion (F) may be present as an impurity in the optional alkali or alkaline earth metal cation (M) source.

The synthesis mixture may optionally further comprise at least one source of halide ions (W), other than 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 example, the halide ions may be present as counter ions of the structure directing agent (Q). Non-limiting examples of halide ion sources include hydrogen chloride, ammonium chloride, hydrogen bromide, ammonium bromide, hydrogen iodide and ammonium iodide; salts containing one or more halide ions, such as metal halides, preferably wherein the metal is sodium, potassium, calcium, magnesium, strontium or barium; ammonium halides; or tetraalkylammonium halides, such as tetramethylammonium halide or tetraethylammonium halide. For example, the arbitrary alkali or alkaline earth metal cation (M) source may also contain small amounts of halide ions (W) as an impurity. The halide ions (W) may be present in a W/Y molar ratio of from 0 to 0.2, for example from 0 to 0.1, for example less than 0.1 or even 0. In a preferred embodiment, the synthesis mixture can be substantially free of halide ions (W).

The synthesis can be performed with or without the addition of nucleating seeds. When nucleating seeds are added to the synthesis mixture, the seeds can be of the same or different structure as the zeolite of the present disclosure or the EMM-70 material from a previous synthesis, and can suitably be present in an amount from about 0.01 ppm to about 10,000 ppm by weight of the synthesis mixture, for example from about 100 ppm to about 5,000 ppm by weight of the synthesis mixture.

Synthetic mixtures typically contain H of 1 to 100, for example 10 to 80 or 15 to 50, for example 20 to 40, for example 25 or 30.₂O/Y molar ratio. Depending on the nature of the components in the base mixture, an amount of solvent (e.g., water from the hydroxide solution, and optionally methanol and ethanol from hydrolysis of the silica source) in the base mixture can be removed so that the desired solvent to Y molar ratio for the synthetic mixture is achieved. Suitable methods for reducing the solvent content include evaporation under a static or flowing atmosphere, such as ambient air, dry nitrogen, dry air, or spray drying or freeze drying. If too much water is removed during the solvent removal process, the desired H₂Water may be added to the resulting mixture to achieve an O/Y molar ratio. In some instances, the formulation is sufficient H₂If the O/Y molar ratio is present, water removal is not necessary.

Carbon in the form of CH ₂ may be present in various sources of the components used to prepare the zeolite of the present disclosure, for example, a tetravalent element source (silica source) or a trivalent element source (alumina source), which may be incorporated into the zeolite framework as a bridging atom. After the SDA is removed, a nitrogen atom may be incorporated into the framework of the zeolite framework as a bridging atom.

In one or more embodiments, after solvent adjustment (e.g., when the desired water to silica ratio is achieved), the synthetic mixture may be mixed by a mechanical process, such as stirring or high shear blending using a dual asymmetric centrifugal mixer (e.g., FlackTek speedmixer) at a mixing speed of 1,000 to 3,000 rpm (e.g., 2000 rpm), to ensure adequate homogenization of the base mixture.

The synthetic mixture is then subjected to suitable crystallization conditions for the formation of the zeolite. Crystallization of the zeolite can be carried out under static or stirred conditions in a suitable reactor vessel, for example a Teflon® lined or stainless steel autoclave placed in a convection oven maintained at a suitable temperature.

The crystallization in step (b) of the method is typically carried out at a temperature of from 100° C. to 200° C., for example from 120° C. to 170° C., for a time sufficient to allow crystallization to occur at the temperature employed. For example, at higher temperatures, the crystallization time may be shortened. For example, the crystallization conditions in step (b) of the method may comprise heating for from 1 day to 100 days, for example from 1 day to 50 days, for example from 10 days or from 20 days to 40 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 X-ray crystallinity and yield of the precipitated solid. Unless otherwise specified herein, the measured temperature 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.

Typically, zeolites are formed in solution and can be recovered by standard means such as centrifugation or filtration. The separated zeolite can also be washed, recovered by centrifugation or filtration, and dried.

The zeolites of the present disclosure, when used as adsorbents or catalysts in organic compound conversion processes, can be at least partially dehydrated (e.g., dried). This can be accomplished by heating at a temperature in the range of 80° C. to 500° C., for example 90° C. to 370° C., for a period of 30 minutes to 48 hours at atmospheric pressure, subatmospheric pressure or superatmospheric pressure under an atmosphere such as air, nitrogen or the like. Dehydration can also be accomplished at room temperature by simply placing the molecular sieve under vacuum, but this requires a longer period of time to obtain a sufficient amount of dehydration.

As a result of the crystallization process, the recovered product contains at least a portion of the structure-directing agent used in the synthesis within the pores. Accordingly, the as-synthesized zeolite recovered in step (c) may be subjected to a heat treatment or other treatment to remove some or all of the SDA incorporated into the pores during the synthesis. The heat treatment (e.g., calcination) of the as-synthesized zeolite typically involves exposing the material to a high temperature sufficient to remove some or all of the SDA in a furnace under an atmosphere selected from air, nitrogen, ozone or mixtures thereof. Subatmospheric pressure may be used for the heat treatment, although atmospheric pressure is preferred for convenience reasons. The heat treatment may be performed at a temperature of up to 925° C., for example, from 300° C. to 700° C. or from 400° C. to 600° C. The temperature measured is the temperature of the sample surrounding the environment. The heat treatment (e.g., calcination) may be performed in a box furnace of dry air, exposed to a drying tube containing a desiccant that removes water from the air. Heating is generally carried out for at least one minute and generally not longer than one day or at most several days. Heating may be carried out initially in a nitrogen atmosphere, and the atmosphere may then be switched to air and/or ozone.

Zeolites can also be ion-exchanged with aqueous ammonium salts, such as ammonium nitrate, ammonium chloride and ammonium acetate, to remove residual alkali metal cations and/or alkaline earth metal cations and replace them with protons to produce an acid form 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. Desirable replacement cations can include hydrogen ions, hydrogen precursors, such as ammonium ions, and mixtures thereof. The ion-exchange step can be performed after the as-synthesized molecular sieve has been dried. The ion-exchange step can be performed before or after the calcination step.

Optionally, in embodiments where the zeolite comprises boron atoms (e.g., where the zeolite is a borosilicate), aluminum atoms may be introduced into the zeolite framework (from which some or all of the SDA has been removed) during an exchange process following the hydrothermal synthesis reaction. This exchange process may comprise exposing the zeolite to a source of aluminum, such as an aqueous solution comprising an aluminum salt, under conditions sufficient to exchange at least some, and substantially all, of the boron atoms in the framework silicate with aluminum atoms. For example, a calcined borosilicate zeolite may be converted to an aluminosilicate by heating the calcined zeolite comprising boron with a solution of aluminum sulfate, aluminum nitrate, aluminum chloride, and/or aluminum acetate (e.g., in a sealed autoclave at 100° C. in a conventional oven or to boiling point in an open system). Afterwards, the aluminized zeolite can be recovered by filtration and washed with deionized water.

Zeolites may also be treated with other treatments, such as steaming and/or solvent washing. Such treatments are well known to those skilled in the art and are carried out to modify the properties of the molecular sieve as desired.

The zeolites of the present disclosure, from which part or all of the SDA has been removed, can be used as adsorbents, or as catalysts or supports for catalysts in a wide variety of hydrocarbon conversions, for example, conversion of organic compounds to converted products.

The zeolites of the present disclosure (wherein some or all of the SDA has been removed) can be used as adsorbents for separating one or more components from a mixture of components in a vapor or liquid phase, for example, having differential sorption properties for a substance. Thus, at least one component can be partially or substantially completely separated from a mixture of components having differential sorption properties for the zeolite by contacting the mixture with the zeolite to selectively sorb one component. For example, in a process for selectively separating one or more desired components of a feedstock from the remaining components of the feedstock, the feedstock can be contacted with a sorbent comprising an aluminosilicate zeolite of the present disclosure under effective sorption conditions to form a sorbed product and an effluent product. One or more of the desired components are recovered from the sorbed product or the effluent product.

The zeolites of the present disclosure (with some or all of the SDA removed) can also be used as catalysts to catalyze various organic compound conversion processes. Examples of chemical conversion processes that are effectively catalyzed by the zeolites described herein, alone or in combination with one or more other catalytically active materials including other crystalline catalysts, include processes that require a catalyst having acid activity. Examples of organic conversion processes that can be catalyzed by the zeolites described herein include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxation, adsorption, alkylation, transalkylation, dealkylation, hydrodecyclization, disproportionation, oligomerization, dehydrocyclization, conversion of methanol to olefins, deNOx applications, and combinations thereof. Conversion of the hydrocarbon feed may be carried out in any convenient manner, depending on the desired process type, such as in a fluidized bed, moving bed or fixed bed reactor.

The zeolites of the present disclosure may be formulated into product compositions by combination with other materials, such as binders and/or matrix materials, which provide additional hardness to the finished product. Such other materials may be inert or catalytically active materials.

For example, it may be desirable to incorporate the zeolites of the present disclosure with other materials that are resistant to the temperatures and other conditions under which they are used. Such materials include synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, metal oxides such as silica and/or alumina, and mixtures thereof. The metal oxides may be naturally occurring or may be in the form of gelatinous precipitates or gels comprising mixtures of silica and metal oxides. The use of a resistant material in combination with the zeolites of the present disclosure (i.e., present or combined during the synthesis of the zeolite in its as-made crystal state in which the crystals are active) tends to alter the conversion and/or selectivity of the catalyst in certain organic conversion processes. The inactive resistant material serves suitably as a diluent to control the amount of conversion in a given process, thereby allowing the product to be obtained in an economical and orderly manner without the use of other means of controlling the reaction rate. Such materials may be incorporated into naturally occurring clays such as bentonite and kaolin to enhance the crush strength of the product under commercial operating conditions. The above-mentioned inert resistive materials, i.e. clay, oxides, etc., function as a binder for the catalyst. A catalyst having good crushing strength may be advantageous in commercial applications, since it is desirable to prevent the catalyst from being crushed into a powdery substance.

Naturally occurring clays which may be used include those of the montmorillonite and kaolin series, including subbentonite, and kaolin, commonly known as Dixie, McNamee, Georgia and Florida clays, or other materials whose major mineral components are halloysite, kaolinite, dickite, nacrite and anoxite. Such clays may be used in the raw state, or after calcination, acid treatment or chemical modification. Binders useful in blending with the zeolites of the present disclosure also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallium oxide, zinc oxide and mixtures thereof.

In addition to the materials mentioned above, the zeolites of the present disclosure can be complexed with porous matrix materials 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.

These binder materials are resistant to temperature and other conditions encountered in various hydrocarbon separation processes, such as mechanical abrasion. Accordingly, the zeolites of the present disclosure can be used in the form of extrudates having a binder. They are typically bound by forming pills, spheres or extrudates. The extrudates are typically formed by extruding a molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudate. Additional treatments such as steaming and/or ion exchange may be performed, if desired. The molecular sieves may optionally be bound with a binder having a surface area of at least 100 m ² /g, for example at least 200 m ² /g, optionally at least 300 m ² /g.

The relative proportions of the molecular sieve and the inorganic oxide matrix can vary widely, the molecular sieve content being in the range of from about 1 wt % to about 100 wt % of the composite, more typically from about 2 wt % to about 95 wt %, and optionally from about 20 wt % to about 90 wt % of the composite, particularly when the composite is prepared in the form of an extrudate.

The zeolites of the present disclosure may also be used in intimate combination with a hydrogenating component (wherein the hydrogenation-dehydrogenation function is performed), such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal (e.g., platinum or palladium). Such hydrogenating components may be incorporated into the composition by one or more of the following processes: co-crystallization; exchanged into the composition to the extent that a Group IIIA element (e.g., aluminum) is present in the structure; or physically intimately mixed. Such components may also be impregnated into or onto the zeolite, for example, by treating the molecular sieve with a hydrogenating metal-containing ion. For example, in the case of platinum, suitable platinum compounds for this purpose include various compounds containing chloroplatinic acid, platinous chloride, and platinum amine complexes. Combinations of metals and methods of introduction thereof may also be used.

Those skilled in the art will appreciate that the zeolites of the present disclosure may contain impurities, such as amorphous materials, unit cells having other topologies (e.g., quartz or other framework type molecular sieves which may or may not affect the performance of the resulting catalyst), and/or other impurities (e.g., heavy metals and/or organic hydrocarbons). Typical examples of different framework type molecular sieves that coexist with the zeolites of the present disclosure are, for example, FAU or IWV framework type molecular sieves, such as faujasite and ITQ-27. The zeolites of the present disclosure are preferably substantially free of impurities. The term "substantially free of impurities" (or alternatively "substantially pure"), as used herein, means that the aluminosilicate zeolite contains minor amounts (less than 50 wt %) of such impurities (e.g., "non-EMM-70 material"), 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 less than 0.1 wt %), wherein the weight percent (wt %) values are based on the combined weight of the impurities and the pure zeolite. The amount of impurities can be determined as appropriate via powder XRD, rotational electron diffraction, and/or SEM/TEM (e.g., by different crystal morphologies).

The zeolites described herein are substantially crystalline. The term "crystalline" as used herein refers to the crystalline solid form of a material, including but not limited to single component or multicomponent crystal forms (e.g., solvates, hydrates, and cocrystals). Crystalline can mean that the molecules have a regular repeating and/or ordered arrangement and have distinguishable crystal lattices. For example, the zeolites can have different water or solvent contents. Different crystal lattices can be identified by solid state characterization methods such as XRD (e.g., powder XRD). Other characterization methods known to those skilled in the art can be helpful in identifying the crystalline form, as well as in determining stability and solvent/water content. The term "substantially crystalline" as used herein means that the majority (greater than 50 wt%) of the sample of the described material is crystalline, with the remainder of the sample being in an amorphous form. In one or more aspects, a substantially crystalline sample has at least 95% crystallinity (e.g., 5% amorphous form), at least 96% crystallinity (e.g., 4% amorphous form), at least 97% crystallinity (e.g., 3% amorphous form), at least 98% crystallinity (e.g., about 2% amorphous form), at least 99% crystallinity (e.g., 1% amorphous form), and 100% crystallinity (e.g., 0% amorphous form).

The embodiments of the present invention are further described by way of specific examples. The following examples are provided for illustrative purposes and are not intended to limit the invention in any way. Those skilled in the art will readily recognize that various parameters may be changed or modified to produce essentially the same results.

Example

The present disclosure is further described below without limiting its scope.

In these examples, X-ray diffraction (XRD) patterns of the as-synthesized and calcined materials were recorded in continuous mode over the 2-theta range from 4° to 36° on an X-ray powder diffractometer (Bruker DaVinci D8 Discovery instrument) using Bragg-Brentano geometry with Cu K _α radiation, a Vantec 500 detector. The interplanar spacing, d-spacing, was calculated in angstroms and the relative intensity of a line, I/I _o , is the ratio of the peak intensity to the intensity of the strongest line above background. The intensity is not corrected for Lorentz and polarization effects. The positions of the diffraction peaks in 2-theta and the relative peak area intensity of the line, I/Io (where Io is the intensity of the strongest line above background), were determined using the MDI Jade peak finding algorithm. It should be understood that diffraction data listed as a single line may consist of multiple overlapping lines which may appear as resolved or partially resolved lines under certain conditions, such as differences in crystallographic variation. Typically, crystallographic variation may include minor changes in unit cell parameters and/or changes in crystal symmetry, without changes in framework connectivity. Such minor effects, including changes in relative intensity, may also arise from differences in cation content, framework composition, pore-filling characteristics and extent, crystal size and shape, preferred orientation, and thermal and/or hydrothermal history.

Scanning electron microscope (SEM) images of the as-synthesized material were obtained with a Hitachi 4800 scanning electron microscope. The SEM images were used to aid in product purity assessment. The presence of distinct crystal forms in the SEM images may be indicative of impurities in other crystalline material forms. This rough analysis can be particularly useful in identifying the presence of relatively small amounts of crystalline impurities that are not identifiable in the product XRD pattern.

The total BET surface area (S _BET ) of a material was determined by the BET method described in the literature [S. Brunauer, et al., J. Am. Chem. Soc. , 1938, v.60, 309] using nitrogen adsorption-desorption at liquid nitrogen temperature, which is herein incorporated by reference. The external surface area (S _ext ) of the material was obtained by the t-plot method, and the micropore surface area (S _micro ) of the material was calculated by subtracting the external surface area (S _ext ) from the total BET surface area (S _BET ).

The micropore volume (V _micro ) of a material can be determined using methods known in the art. For example, the micropore volume of a material can be measured by nitrogen physisorption and the data can be analyzed by the t-plot method described in Lippens, BC et al., "Studies on pore system in catalysts: V. The t method", J. Catal. , v.4, 319 (1965), which describes the micropore volume method and is herein incorporated by reference.

The molar ratios and conditions used in the synthesis of Examples 2 to 7 and the products formed are described in detail below and summarized in Table 3.

Example 1a: 1,2,3-Trimethyl-4,5,6,7-tetrahydro-1 H -Benzo[ d ]Synthesis of imidazole-3-ium cation (SDA-1)

2-Methyl-4,5,6,7-tetrahydro-1H-benzimidazole: 40 g of 2-methylbenzimidazole was dissolved in 320 mL of glacial acetic acid. 15 g of palladium (10 wt% on carbon) was added and the reaction mixture was treated with hydrogen at 120 °C and 80 bar pressure for 24 h. The solution was filtered over celite and washed with glacial acetic acid. The solvent was evaporated in vacuo and sodium hydroxide solution was added to bring the pH of the solution to 9-10. The precipitate was filtered, washed with water, dissolved in chloroform and extracted with saturated sodium chloride solution. The organic phase was dried over sodium sulfate, filtered and concentrated in vacuo.

1,2,3-Trimethyl-4,5,6,7-tetrahydro-1 H -benzo[ d ]imidazol-3-ium iodide: 13.6 g of 2-methyl-4,5,6,7-tetrahydro-1 H -benzimidazole, 70 g of iodomethane and 27 g of potassium carbonate were added to 150 mL of acetonitrile (CH ₃ CN) in a 250 mL round-bottom flask equipped with a magnetic stir bar. The suspension was then refluxed for 18 h and then cooled to room temperature. The solution was then filtered through a Buchner funnel, and the filtrate was concentrated using a rotovap. Dichloromethane was added to the concentrated solution to remove the remaining potassium salt. The filtrate in dichloromethane was concentrated using a rotary evaporator and dried under vacuum to obtain 1,2,3-trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium iodide.

1,2,3-Trimethyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazol-3-ium hydroxide: The iodide salt was ion-exchanged into hydroxide form by ion-exchange resin Amberlite® IRN78 OH in hydroxide form (iodide:resin:water ratio of 1:3.5:5). The exchange was carried out overnight at room temperature.

Example 1b: 2-Ethyl-1,3-dimethyl-4,5,6,7-tetrahydro-1 H -Synthesis of benzo[d]imidazole-3-ium cation (SDA-2)

The three-step process of Example 1a was followed except that 2-methylbenzimidazole was replaced with 2-ethylbenzimidazole.

Example 2: SDA-1, USY zeolite, Si/Al=15

In a PTFE liner for a 23 mL Steel Parr autoclave, 2.87 g (13.9 wt%) of SDA-1 solution, 0.72 g (4 wt%) of NaOH solution, 2.16 g of deionized water, and 0.190 g of Ultrastable Y (USY) zeolite having a Si/Al molar ratio of 15 (available as CBV720 from Zeolyst) were mixed together to form a synthetic mixture having the following molar ratio composition:

25 H ₂ O : 1 SiO ₂ : 0.033 Al ₂ O ₃ : 0.23 QOH : 0.07 NaOH.

The liner was then capped and sealed in a 23 mL Parr autoclave and placed in a spit inside a convection oven. The reactor was heated at 160°C for 6 weeks under tumbling conditions (approximately 30 rpm). The product was isolated by filtration, rinsed with deionized water, and dried. The as-synthesized material was then calcined in air to 580°C in a box furnace at a ramping rate of 3°C/min. The temperature was maintained at 580°C for 8 hours and then the box furnace was allowed to cool.

XRD analysis of the as-synthesized and calcined material showed that the material had similar powder XRD patterns to as-synthesized and calcined SSZ-64, respectively, in terms of 2-theta and d-spacing, but different relative intensities (see tables I/IA and II/IIA of WO 2004/013042 A1). The new product was named EMM-70. Figure 1 shows a SEM image of the as-synthesized product. The exact structure of EMM-70 is not known.

The micropore surface area (S _micro ) of the calcined version of the EMM-70 material was 505 m ² /g, the external surface area (S _ext ) was 63 m ² /g, and the micropore volume (V _micro ) was 0.18 cc/g.

Example 3: SDA-1, USY zeolite, Si/Al=15

This example was carried out under the same conditions as Example 2 except that the synthetic mixture contained a greater amount of SDA-1 and a lesser amount of NaOH, and a composition having the following molar ratio was obtained:

25 H ₂ O : 1 SiO ₂ : 0.033 Al ₂ O ₃ : 0.40 QOH : 0.05 NaOH.

After heating at 160°C for 4 weeks, pure EMM-70 product was obtained as confirmed by XRD pattern.

Comparative Example 4: SDA-1, USY zeolite, Si/Al=30

This example was carried out under the same conditions as Example 1 except that USY zeolite (available as CBV760 from Zeolyst) having a Si/Al molar ratio of 30 was used as the Si and Al source, resulting in a Si/Al molar ratio of 30 in the synthetic mixture. EMM-70 was not obtained even after heating at 160 °C for 4 weeks. The resulting product was identified as ITQ-27 based on its XRD pattern as disclosed in the literature [JE Schmidt et al. (2016) Chem. Eur. J. , v.22, pp. 4022-4029] or WO 2006/055305 A2.

Example 5: SDA-2, USY zeolite, Si/Al=15

The same conditions as in Example 1 were followed, except that SDA-1 was replaced with SDA-2 and the Q/Si molar ratio was 0.25 instead of 0.23. After heating at 160°C for 4 weeks, pure EMM-70 product was obtained, as confirmed by XRD pattern. FIGS. 2 and 3 show powder XRD patterns of the as-synthesized and calcined products of Example 5. Tables 4 and 5 below show peak and intensity lists for the as-synthesized and calcined EMM-70 products of Example 5. FIG. 4 shows an SEM image of the as-synthesized product of Example 5.

Example 6: SDA-2, USY zeolite, Si/Al=15

This example was carried out under the same conditions as Example 5 except that the synthetic mixture contained different amounts of SDA-2, NaOH and water, resulting in compositions having the following molar ratios:

30 H ₂ O : 1 SiO ₂ : 0.033 Al ₂ O ₃ : 0.20 QOH : 0.10 NaOH.

After heating at 160°C for 5 weeks, EMM-70 product containing a small amount of ITQ-27 was obtained as confirmed by XRD pattern.

Example 7: SDA-2, colloidal silica, sodium aluminate, Si/Al=15

This example was conducted under the same conditions as Example 6, except that Ludox HS40 (40 wt% colloidal silica suspension) was used as the Si source and sodium aluminate (NaAlO ₂ , 25 wt% Al ₂ O ₃ , 19.3 wt% Na ₂ O) was used as the Al source. NaOH was also present at a slightly higher Na/Si molar ratio of 0.15. After heating at 160°C for 5 weeks, EMM-70 product containing a small amount of ITQ-27 was obtained, as confirmed by XRD pattern.

Example 8: SDA-2, USY zeolite, Si/Al=15

This example was carried out under the same conditions as Example 5 except that the synthetic mixture contained a higher amount of SDA-2 and was carried out without NaOH, resulting in a composition having the following molar ratio:

25 H ₂ O : 1 SiO ₂ : 0.033 Al ₂ O ₃ : 0.35 QOH.

After heating at 160°C for 3 weeks, EMM-70 product was obtained with undissolved faujasite zeolite phase as confirmed by XRD pattern.

[Table 3]

* SDA-1 = 1,2,3-trimethyl-4,5,6,7-tetrahydro-1 H -benzo[ d ]imidazol-3-ium cation

** SDA-2 = 2-Ethyl-1,3-dimethyl-4,5,6,7-tetrahydro-1 H -benzo[ d ]imidazol-3-ium cation

[Table 4]

[Table 5]

While the present disclosure has been described and illustrated with reference to specific embodiments, it will be appreciated by those skilled in the art that many other changes, modifications, and variations can be made to the present invention that are 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. Furthermore, all numerical values in the detailed description herein are modified to "about" the stated value, and take into account experimental errors and deviations that can be expected by those skilled in the art.

Wherever in the foregoing description, integers or elements having known, obvious or foreseeable equivalents are mentioned, such equivalents are incorporated herein as if individually set forth. Reference should be made to the claims for determining the true scope of the invention, which should be construed to encompass any such equivalents. It will also be understood by the reader that integers or features of the invention described as preferred, advantageous, convenient, etc., are optional and do not limit the scope of the independent claims. Furthermore, it should be understood that such optional integers or features, while providing a possible advantage in some embodiments of the invention, may not be preferred and thus absent in other embodiments.

Additionally or alternatively, the present disclosure relates to:

Embodiment 1: A zeolite having an X-ray diffraction pattern comprising peaks of Table 1 or 1A in calcined form.

Embodiment 2: In embodiment 1,

A zeolite having the molecular formula of the following chemical formula II:

(m)X₂O₃:YO₂ (Chemical Formula II)

In the above formula, 0.017 ≤ m ≤ 0.1; X is a trivalent element; and Y is a tetravalent element.

Embodiment 3: In embodiment 2,

A zeolite wherein X comprises at least one of aluminum and boron, preferably X is selected from the group consisting of aluminum, boron, or a combination thereof, and more preferably X comprises or is aluminum.

Embodiment 4: In embodiment 2 or 3,

A zeolite wherein Y comprises at least one of silicon and germanium, preferably Y is selected from the group consisting of silicon, germanium, or a combination thereof, and more preferably Y comprises or is silicon.

Embodiment 5: A zeolite having an X-ray diffraction pattern comprising peaks of Table 2 or 2A in as-synthesized form.

Embodiment 6: In embodiment 5,

A zeolite having the molecular formula of the following chemical formula III:

(q)Q : (m)X ₂ O ₃ : YO ₂ (chemical formula III)

In the above formula,

0 ≤ q ≤ 0.5; 0.017 ≤ m ≤ 0.1;

Q comprises one or more cations selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following formula I:

(chemical formula I)

In the above formula, R is methyl or ethyl; X is a trivalent element; and Y is a tetravalent element.

Embodiment 7: In embodiment 6,

A zeolite wherein X comprises at least one of aluminum and boron, preferably X is selected from the group consisting of aluminum, boron, or a combination thereof, and more preferably X comprises or is aluminum.

Embodiment 8: In embodiment 6 or 7,

A zeolite wherein Y comprises at least one of silicon and germanium, preferably Y is selected from the group consisting of silicon, germanium, or a combination thereof, and more preferably Y comprises or is silicon.

Embodiment 9: In any one of embodiments 6 to 7,

A zeolite, wherein the structure-directing agent (Q) comprises at least one cation selected from the group consisting of a 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, a 2-ethyl-1,3-dimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, and mixtures thereof.

Embodiment 10: In any one of embodiments 1 to 9,

A zeolite which is an aluminosilicate or a borosilicate; having a Si/Al or Si/B molar ratio of less than 30, preferably from 5 to 25, more preferably from 10 to 25.

Embodiment 11: A method for producing a zeolite according to any one of embodiments 1 to 10,

(a) a step of preparing a synthetic mixture comprising water, a source of a tetravalent element (Y) oxide, a source of a trivalent element (X) oxide, a structure-directing agent (Q), optionally a source of hydroxide ions (OH), and optionally a source of an alkali and/or alkaline earth metal element (M),

The above structural inducer (Q) comprises at least one cation selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following chemical formula I:

(chemical formula I)

[In the above formula, R is methyl or ethyl];

wherein the synthetic mixture has a Y/X molar ratio of less than 30, and if a fluoride (F) source is present, the F/Y molar ratio is less than 0.05;

(b) heating the synthetic mixture under crystallization conditions including a temperature of 100 to 200° C. for a time sufficient to form crystals of the zeolite;

(c) recovering at least a portion of the zeolite from step (b); and

(d) optionally, a step of treating the zeolite recovered in step (c) to remove at least a portion of the structure-directing agent (Q).

A method including:

Embodiment 12: In embodiment 11,

A method wherein the structure-inducing agent (Q) comprises at least one cation selected from the group consisting of 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, 2-ethyl-1,3-dimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, and mixtures thereof.

Embodiment 13: In embodiment 11 or 12,

A method wherein the structural inducer (Q) is in the form of a halide, a hydroxide, or a nitrate, preferably in the form of a hydroxide.

Embodiment 14: In any one of embodiments 11 to 13,

A method wherein the trivalent element X comprises at least one of aluminum or boron, preferably X is selected from the group consisting of aluminum, boron, or a combination thereof, more preferably X comprises or is aluminum, and the tetravalent element Y comprises at least one of silicon or germanium, preferably Y is selected from the group consisting of silicon, germanium, or a combination thereof, more preferably Y comprises or is silicon.

Embodiment 15: In any one of embodiments 11 to 14,

A method wherein a synthetic mixture has the following composition in terms of molar ratio.

Embodiment 16: In any one of embodiments 11 to 15,

A method wherein said synthetic mixture comprises a fluoride (F) source in a F/Y molar ratio of 0 to 0.02, preferably 0 to 0.01, and most preferably wherein the synthetic mixture is substantially free of fluoride (F) ions.

Embodiment 17: A method of converting an organic compound into a conversion product, comprising contacting the organic compound with a zeolite of any one of Embodiments 1 to 10.

Claims (13)

A zeolite having an X-ray diffraction pattern comprising peaks set forth in Table 1 below, in calcined form.
[Table 1]
In the first paragraph,
A zeolite having the molecular formula of the following chemical formula II:
(m)X₂O₃:YO₂ (Chemical Formula II)
In the above formula,
0.017 ≤ m ≤ 0.1;
X is a trivalent element; Y is a tetravalent element; in particular,
X comprises at least one of aluminum or boron, preferably X comprises or is aluminum;
Y comprises at least one of silicon and germanium, preferably Y comprises silicon or is silicon. A zeolite having an X-ray diffraction pattern comprising peaks set forth in Table 2 below, in as-synthesized form.
[Table 2]
In the third paragraph,
A zeolite having the molecular formula of the following chemical formula III:
(q)Q : (m)X ₂ O ₃ : YO ₂ (chemical formula III)
In the above formula,
0 ≤ q ≤ 0.5; 0.017 ≤ m ≤ 0.1;
Q comprises one or more cations selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following formula I:
(chemical formula I)
[In the above formula, R is methyl or ethyl];
X is a trivalent element; Y is a tetravalent element; in particular,
X comprises at least one of aluminum or boron, preferably X comprises or is aluminum;
Y comprises at least one of silicon and germanium, preferably Y comprises silicon or is silicon. In paragraph 4,
A zeolite, wherein the structure-directing agent (Q) comprises at least one cation selected from the group consisting of a 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, a 2-ethyl-1,3-dimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, and mixtures thereof. In any one of paragraphs 1 to 5,
A zeolite which is an aluminosilicate or a borosilicate; having a Si/Al or Si/B molar ratio of less than 30, preferably from 5 to 25, more preferably from 10 to 25. A method for producing a zeolite according to any one of claims 1 to 6,
(a) a step of preparing a synthetic mixture comprising water, a source of a tetravalent element (Y) oxide, a source of a trivalent element (X) oxide, a structure-directing agent (Q), optionally a source of hydroxide ions (OH), and optionally a source of an alkali and/or alkaline earth metal element (M),
The above structural inducer (Q) comprises at least one cation selected from 4,5,6,7-tetrahydrobenzimidazolium cations of the following chemical formula I:
(chemical formula I)
[In the above formula, R is methyl or ethyl];
wherein the synthetic mixture has a Y/X molar ratio of less than 30, and if a fluoride (F) source is present, the F/Y molar ratio is less than 0.05;
(b) heating the synthetic mixture under crystallization conditions including a temperature of 100 to 200° C. for a time sufficient to form crystals of the zeolite;
(c) recovering at least a portion of the zeolite from step (b); and
(d) optionally, a step of treating the zeolite recovered in step (c) to remove at least a portion of the structure-directing agent (Q).
A method including: In Article 7,
A method wherein the structure-inducing agent (Q) comprises at least one cation selected from the group consisting of 1,2,3-trimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, 2-ethyl-1,3-dimethyl-4,5,6,7-tetrahydrobenzimidazolium cation, and mixtures thereof. In clause 7 or 8,
A method wherein the structural inducer (Q) is in the form of a halide, a hydroxide, or a nitrate, preferably in the form of a hydroxide. In any one of Articles 7 to 9,
The above trivalent element X is selected from the group consisting of aluminum, boron and mixtures thereof, and is preferably aluminum,
A method wherein the above four elements Y are selected from the group consisting of silicon, germanium and mixtures thereof, and are preferably silicon. In any one of Articles 7 to 10,
A method wherein the synthetic mixture has the following composition in terms of molar ratio.
In any one of Articles 7 to 11,
A method wherein said synthetic mixture comprises a fluoride (F) source in a F/Y molar ratio of 0 to 0.02, preferably 0 to 0.01, and most preferably wherein the synthetic mixture is substantially free of fluoride (F) ions. A method for converting an organic compound into a conversion product, comprising contacting the organic compound with a zeolite of any one of claims 1 to 6.