Molecular sieve SSZ-124, its synthesis and use

Abstract

The present disclosure relates to an aluminogermanosilicate molecular sieve material designated SSZ-124, methods for making same, and uses thereof.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 421,220, filed November 1, 2022, the disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates to a novel aluminogermanosilicate molecular sieve material designated SSZ-124, methods for making same, and uses thereof. [Background technology]

[0003] Both natural and synthetic molecular sieve materials can be used as adsorbents and have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, are ordered, porous, crystalline materials with distinct crystalline structures as determined by X-ray diffraction (XRD). Certain molecular sieves are ordered and produce specific, identifiable XRD patterns. Numerous cavities may exist within certain molecular sieve materials, which may be interconnected by numerous channels or pores. These cavities and pores are uniform in size within certain molecular sieve materials. Because the dimensions of these pores allow for the acceptance of adsorbed molecules of a specific size while excluding adsorbed molecules of larger sizes, these materials have become known as "molecular sieves" and are utilized in various industrial processes (e.g., cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization).

[0004] Molecular sieves used in catalysis and adsorption applications include either natural or synthetic crystalline molecular sieves. Examples of these molecular sieves include large-pore zeolites, medium-pore zeolites, and small-pore zeolites. These zeolites and their isotypes are classified by the Structure Commission of the International Zeolite Association (IZA) according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, framework zeolites and other crystalline microporous molecular sieves with established structures are assigned three-letter codes, which are listed in "Atlas of Zeolite Framework Types," eds. Ch. Baerlocher, L.B. McCusker, and D.H. Olson, Elsevier, Sixth Revised Edition, 2007, incorporated herein by reference. These zeolites and their isotypes are also listed in the IZA Structure Commission's "Database of Zeolite Structures."

[0005] Although many different crystalline molecular sieves have been discovered, there is a continuing need for new molecular sieves with desirable properties for gas separation and drying, organic conversion reactions, and other applications. New molecular sieves may contain novel internal pore structures, leading to improved selectivity in these processes. Summary of the Invention

[0006] The present disclosure relates to aluminogermanosilicate molecular sieves, methods for making same, and uses thereof.

[0007] In one embodiment, the present disclosure relates to a synthetic crystalline aluminogermanosilicate molecular sieve, which in its as-calcined form (e.g., with at least a portion of the structure directing agent removed), has a powder X-ray diffraction pattern including at least the peaks listed in the table below. [Table 1]

[0008] In a second embodiment, the present disclosure relates to a synthetic crystalline aluminogermanosilicate molecular sieve that, in its as-synthesized form (e.g., without structure directing agents removed), has a powder X-ray diffraction pattern that includes at least the peaks listed in the table below. [Table 2]

[0009] In a third embodiment, the present disclosure provides a method for producing an aluminogermanosilicate molecular sieve, comprising: (1) combining (a) an aluminosilicate molecular sieve having an FAU framework structure; (b) a germanium source; (c) N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 (d) a structure directing agent comprising 3a,6a-octamethyloctahydropentalene-2,5-diammonium cation; (e) a fluoride ion source; and (f) water; and (g) heating the reaction mixture to obtain an aluminogermanosilicate molecular sieve, wherein the aluminogermanosilicate molecular sieve has a framework structure different from that of an aluminosilicate molecular sieve.

[0010] In a fourth embodiment, the present disclosure relates to a process for converting an organic compound to a conversion product, comprising contacting the organic compound with an aluminogermanosilicate molecular sieve according to the first or second embodiment, or prepared according to the method of the third embodiment. [Brief explanation of the drawings]

[0011] [Figure 1] 1A and 1B show scanning electron microscope (SEM) images of the as-synthesized product of Example 1 at different magnifications.

[0012] [Figure 2] FIG. 2 shows the powder X-ray diffraction (XRD) pattern of the calcined molecular sieve product of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present disclosure relates to an alumino-germanosilicate molecular sieve, a method for making the same, and uses thereof. The alumino-germanosilicate molecular sieve may also be referred to as SSZ-124 molecular sieve or SSZ-124 material.

[0014] definition The term "aluminosilicate" refers to a molecular sieve material having a framework structure built from alumina and silica (i.e., repeating tetrahedral units of AlO4 and SiO4).

[0015] The term "aluminogermanosilicate" refers to a molecular sieve material having a framework structure built with alumina, germania, and silica (i.e., repeating tetrahedral units of AlO4, GeO4, and SiO4).

[0016] The term "FAU" refers to an FAU-type topology or framework as recognized by the Structure Commission of the International Zeolite Association (IZA), and the term "FAU molecular sieve" means an aluminosilicate whose primary crystalline phase is FAU.

[0017] The "as-synthesized" (or "as-produced") aluminogermanosilicate molecular sieves of the present disclosure (i.e., before heat treatment or other treatment to remove the structure directing agent from the pores) typically contain within their pores a structure directing agent that was one of the components of the reaction mixture. Aluminogermanosilicate molecular sieves of the present disclosure from which some or all of the structure directing agent has been removed (e.g., via heat treatment or other treatment to remove the structure directing agent from the pores) are at least partially calcined, or "as-calcined" materials.

[0018] Molecular sieve synthesis Generally, the aluminogermanosilicate molecular sieve of the present disclosure comprises: (1) (a) an aluminosilicate molecular sieve having an FAU framework structure; (b) a germanium source; (c) N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 The aluminogermanosilicate molecular sieve can be synthesized by (i) preparing a reaction mixture containing (a) a structure directing agent [Q] comprising 3a,6a-octamethyloctahydropentalene-2,5-diammonium cation, (b) a fluoride ion source, and (c) water; and (d) heating the reaction mixture to obtain an aluminogermanosilicate molecular sieve, wherein the aluminogermanosilicate molecular sieve has a framework structure different from that of the aluminosilicate molecular sieve.

[0019] Aluminogermanosilicate molecular sieves can be prepared from reaction mixtures having compositions within the ranges shown in Table 1 in terms of molar ratios. [Table 1]

[0020] The aluminosilicate molecular sieve having an FAU framework structure may be a single type of FAU molecular sieve or a mixture of two or more FAU molecular sieves. In certain embodiments, the FAU molecular sieve may be zeolite Y. The FAU molecular sieve may be two or more Y-zeolites having different silica to alumina molar ratios. The FAU molecular sieve may be in the hydrogen form (H + form), ammonium form (NH4 + form), or a combination of these forms.

[0021] Suitable sources of germanium include germanium oxide, germanium nitrate, and germanium alkoxides, (eg, tetraethoxygermanium).

[0022] Suitable sources of fluoride ions include one or more of hydrogen fluoride (HF), ammonium fluoride (NH4F), and ammonium bifluoride (NH4HF2).

[0023] The structure directing agent [Q] is represented by the following structure (1): 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene-2,5-diammonium cation. [ka]

[0024] The structure directing agent [Q] may be present in any suitable form, for example as a halide such as iodide or bromide, or as a hydroxide, for example in its hydroxide form.

[0025] The synthesis may be carried out with or without the addition of nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds may be of the same or different structure as the aluminogermanosilicate molecular sieve of the present disclosure or the SSZ-124 material, and may be present in an amount of 0.1 to 10 wt. % based on 100 wt. % SiO2 in the framework structure of the aluminosilicate FAU molecular sieve, preferably 0.5 to 5 wt. % based on 100 wt. % SiO2 in the framework structure of the aluminosilicate FAU molecular sieve.

[0026] The reaction mixture can be prepared by any conceivable means, but mixing by agitation, preferably stirring, is preferred. The reaction mixture can be prepared in batch mode, continuous mode, or semi-continuous mode.

[0027] The reaction mixture may be in the form of a solution, a colloidal dispersion (colloidal sol), a gel, or a paste, with a gel being preferred.

[0028] The reaction mixture is then subjected to suitable crystallization conditions to form the aluminogermanosilicate molecular sieve. The crystallization of the aluminogermanosilicate molecular sieve can be carried out under static or stirred conditions in a suitable reaction vessel, such as, for example, a Teflon-lined or stainless steel autoclave placed in a convection oven maintained at a suitable temperature.

[0029] Crystallization is generally carried out at a temperature of 100°C to 200°C (e.g., 120°C to 170°C) for a time sufficient for crystallization to occur at the temperature used. For example, at higher temperatures, crystallization times may be shortened. For example, crystallization conditions may include heating for a period of 1 day to 30 days (e.g., 1 day to 14 days, or 1 day to 7 days). Preferably, the synthesis is carried out under autogenous pressure, preferably in an autoclave.

[0030] Typically, the alumino-germanosilicate molecular sieve is formed in solution and can be recovered by any known separation technique, such as decantation, filtration, ultrafiltration, centrifugation, or any other solid-liquid separation technique, and combinations thereof. The recovered solids can then be washed with deionized or purified water and dried at elevated temperatures for several hours. The drying step can be carried out under vacuum or atmospheric pressure.

[0031] In the drying step, moisture is removed from the aluminogermanosilicate molecular sieve after the crystallization step or the washing step. The conditions for the drying step are arbitrary, but one example is to dry the molecular sieve by leaving it in an environment at a temperature of 50°C or higher and 150°C or lower for at least 2 hours (e.g., 4 to 24 hours) after the crystallization step or the washing step.

[0032] As a result of the crystallization process, the recovered as-synthesized molecular sieve product contains within its pores at least a portion of the structure-directing agent used in the synthesis. Thus, the as-synthesized aluminogermanosilicate molecular sieve can be subjected to heat treatment or other treatment to remove some or all of the structure-directing agent incorporated into its pores during synthesis. Heat treatment (e.g., calcination) of the as-synthesized aluminogermanosilicate molecular sieve typically involves exposing the material to a high temperature sufficient to remove some or all of the structure-directing agent, preferably in an oxygen-containing atmosphere (e.g., air) in a furnace. Heat treatment can be carried out at temperatures between 400°C and 700°C (e.g., 450°C and 600°C). Heat treatment can be carried out for at least 1 hour, typically up to 20 hours (e.g., 2 to 10 hours, or 3 to 7 hours). Heating can be carried out initially under a nitrogen atmosphere up to 400°C, followed by switching the atmosphere to air at 400°C and 700°C.

[0033] Molecular sieve characterization The aluminogermanosilicate molecular sieve of the present disclosure can have a SiO2 / Al2O3 molar ratio of 50 or greater (eg, 50 to 500, or 100 to 500, or 50 to 250, or 100 to 250).

[0034] The aluminogermanosilicate molecular sieve of the present disclosure can have a SiO / GeO molar ratio in the range of 0.1 to 30 (e.g., 0.25 to 20, or 0.5 to 15, 5 to 10, or 1 to 5). The SiO / AlO and SiO / GeO molar ratios of the zeolite can be determined by conventional analysis.

[0035] The crystals of the aluminogermanosilicate molecular sieve can have a d50 crystal size of 5 μm or less (e.g., 0.5 μm to 5 μm).

[0036] Crystal size is based on individual crystals (including twins) but does not include crystal agglomerates. Crystal size is the length of the longest diagonal of a three-dimensional crystal. Direct measurements of crystal size can be made using microscopy techniques such as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). For example, SEM measurements involve examining the morphology of a material at high magnification (typically 1000x to 100,000x). SEM can be performed by distributing a representative portion of molecular sieve powder on a suitable mount so that individual particles are reasonably evenly spread across the entire field of view at 1000x to 100,000x magnification. From this population, a statistically significant sample of random individual crystals (e.g., 50-200) is examined, and the longest diagonal of each individual crystal is measured and recorded. Particles that are clearly large polycrystalline agglomerates should not be included in the measurement. Based on these measurements, the d50 of the crystal size of the sample is calculated.

[0037] The as-synthesized aluminogermanosilicate molecular sieve (e.g., without heat treatment) has a characteristic powder XRD pattern that includes at least the lines listed in Table 2. [Table 2]

[0038] The as-calcined aluminogermanosilicate molecular sieve (eg, with at least a portion of the structure directing agent removed) has a characteristic powder XRD pattern including at least the peaks set forth in Table 3. [Table 3]

[0039] Powder X-ray diffraction patterns were determined by standard techniques. The radiation was copper K-alpha / doublet, and a scintillation counter spectrometer equipped with a strip chart pen recorder was used. Peak heights, I, in degrees 2-theta (2θ), where θ is the Bragg angle, and their positions were read from the spectrometer chart. From these measurements, the relative intensity, 100I / I0, where I0 is the intensity of the most intense line or peak, and d, the interplanar spacing in angstroms corresponding to the recorded line, can be calculated. Relative intensities are based on the most intense line in the X-ray pattern, which is assigned a value of 100. Relative intensities are designated by the following designations: VS = very strong (greater than 60 to 100), S = strong (greater than 40 to 60), M = moderate (greater than 20 to 40), and W = weak (less than 20). The reported d-spacing values, when converted to corresponding values ​​for d-spacing using Bragg's law, have a corresponding deviation determined based on ±0.20 degrees 2θ.

[0040] Minor variations in the diffraction pattern values ​​in the tables or figures may result, for example, from variations in the nature and degree of pore filling, framework composition, and crystallite size and shape. Despite these minor perturbations, the basic crystalline structure of the as-prepared and as-calcined materials remains substantially unchanged.

[0041] The aluminogermanosilicate molecular sieves of the present disclosure may contain impurities such as amorphous materials, unit cells with different topologies (e.g., quartz or molecular sieves of different framework types that may or may not affect the performance of the resulting catalyst), and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). The aluminogermanosilicate molecular sieves of the present disclosure are preferably substantially free of impurities. As used herein, the term "substantially free of impurities" (or alternatively, "substantially pure") means that the aluminogermanosilicate molecular sieve contains a small proportion (less than 50 wt.%) of such impurities, 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.%), where the weight percent (wt.%) value is based on the combined weight of the impurities and the pure aluminogermanosilicate molecular sieve. The amount of impurities can be suitably determined by powder XRD, rotational electron diffraction, and / or SEM / TEM (eg, different crystalline forms).

[0042] The aluminogermanosilicate molecular sieves described herein are substantially crystalline. As used herein, the term "crystalline" refers to a crystalline solid form of a material, including single-component or multi-component crystalline forms (e.g., including solvates, hydrates, and co-crystals). Crystallinity can mean having a regular repeating and / or ordered arrangement of molecules, as well as having a distinguishable crystal lattice. For example, aluminogermanosilicate molecular sieves can have different water or solvent contents. The 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 further aid in identifying the crystalline form, as well as determining stability and solvent / water content. As used herein, the term "substantially crystalline" means that the majority (greater than 50% by weight) of the weight of a sample of the described material is crystalline, with the remainder of the sample being in an amorphous form. In one or more embodiments, 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., 2% amorphous form), at least 99% crystallinity (e.g., 1% amorphous form), and 100% crystallinity (e.g., 0% amorphous form).

[0043] Use of Alumino-germanosilicate Molecular Sieve The aluminogermanosilicate molecular sieves of the present disclosure, from which some or all of the structure directing agent has been removed, can be used as adsorbents or as catalysts or catalyst supports in a wide variety of hydrocarbon conversions (e.g., the conversion of organic compounds to converted products). Thus, the present disclosure relates to the use of the aluminogermanosilicate molecular sieves described herein as adsorbents or as catalysts or catalyst supports in hydrocarbon conversions. The present disclosure also relates to a process for converting organic compounds to conversion products, comprising contacting the organic compounds with the aluminogermanosilicate molecular sieves described herein.

[0044] The aluminogermanosilicate molecular sieves of the present disclosure (from which some or all of the structure-directing agent has been removed) can be used as adsorbents, such as for separating at least one component from a mixture of components in a vapor or liquid phase having different sorption properties for the materials. Thus, at least one component can be partially or substantially completely separated from a mixture of components having different sorption properties for the aluminogermanosilicate molecular sieve by contacting the mixture with the aluminogermanosilicate molecular sieve to selectively sorb the one component. For example, in a process for selectively separating one or more desired components of a feed material from the remaining components of the feed material, the feed material can be contacted with a sorbent comprising the aluminogermanosilicate molecular sieve of the present disclosure under effective sorption conditions, thereby forming a sorbed product and an effluent product. One or more of the desired components can be recovered from either the sorbed product or the effluent product.

[0045] The aluminogermanosilicate molecular sieves of the present disclosure (with some or all of the structure directing agent removed) can also be used as catalysts to catalyze a wide variety of organic compound conversion processes. Examples of chemical conversion processes that can be effectively catalyzed by the aluminogermanosilicate molecular sieves described herein, alone or in combination with one or more other catalytically active materials (including other crystalline catalysts), include those requiring a catalyst with acid activity. Examples of organic conversion processes that can be catalyzed by the aluminogermanosilicate molecular sieves described herein include cracking, hydrocracking, isomerization, oligomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, alkylation, transalkylation, dealkylation, disproportionation, hydrogenation ring-opening, dehydrogenation ring-opening, methanol to olefins, deNO x The conversion of the hydrocarbon feed can be carried out in any convenient manner, for example in a fluidized bed, moving bed, or fixed bed reactor, depending on the type of process desired.

[0046] The aluminogermanosilicate molecular sieves of the present disclosure can be formulated into product compositions by combining them with other materials, such as binders and / or matrix materials, that impart additional hardness to the finished product. These other materials can be inert or catalytically active materials.

[0047] For example, it may be desirable to blend the aluminogermanosilicate molecular sieves of the present disclosure with another material that can withstand the temperatures and other conditions encountered during use. Such materials include synthetic or natural 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 natural or may be in the form of gelatinous precipitates or gels containing mixtures of silica and metal oxides. The use of crystalline active, resistant materials (i.e., combined with or present during the synthesis of the as-synthesized aluminogermanosilicate molecular sieves) in combination with the aluminogermanosilicate molecular sieves of the present disclosure tends to alter the conversion and / or selectivity of the catalyst in certain organic conversion processes. The inert, resistant materials preferably function as diluents to control the amount of conversion in a given process so that products can be obtained in an economical and orderly manner without employing other means to control the reaction rate. These materials can be incorporated into natural clays (e.g., bentonite and kaolin) to improve the crush strength of the product under commercial operating conditions. These inert, resistant materials (i.e., clays, oxides, etc.) act as binders for the catalyst. In commercial applications, it is desirable to prevent the catalyst from breaking down into powder-like materials, so a catalyst with good crush strength can be beneficial.

[0048] Natural clays that can be used include the montmorillonite and kaolin families, including sub-bentonite and kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays, or others whose primary mineral composition is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used as originally mined or after calcination, acid treatment, or chemical modification. Binders useful for compositing the aluminogermanosilicate molecular sieves of the present disclosure also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallium oxide, zinc oxide, and mixtures thereof.

[0049] In addition to the materials mentioned above, the alumino-germanosilicate molecular sieves of the present disclosure can be composited with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0050] These binder materials are resistant to temperatures and other conditions (e.g., mechanical wear) encountered in various hydrocarbon conversion processes. Therefore, the aluminogermanosilicate molecular sieves of the present disclosure can be used in the form of extrudates combined with a binder. They are typically bound by forming pills, spheres, or extrudates. The extrudates are typically formed by extruding the molecular sieve, optionally in the presence of a binder, drying the resulting extrudates, and subsequently calcining them. Optionally, further processing, such as steaming and / or ion exchange, may be performed. The molecular sieves are optionally bound to a matrix of at least 100 m 2 / g (e.g., at least 200 m 2 / g, or at least 300m 2 / g) of surface area.

[0051] The relative proportions of aluminogermanosilicate molecular sieve and inorganic oxide matrix can vary widely, with the aluminogermanosilicate molecular sieve content ranging from 1 to 99 wt. % of the composite, more typically from 2 to 95 wt. %, and optionally from 20 to 90 wt. %, particularly when the composite is prepared in the form of an extrudate. [Example]

[0052] The following illustrative examples are intended to be non-limiting.

[0053] Example 1 A tared cup with cap and cap weight was added to the tared cup with cap and 2.5 mmol of N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene 2,5-diammonium dihydroxide was added along with the following solids: 0.27 grams of Tosoh 390HUA Y-zeolite (H + -form, SiO2 / Al2O3 molar ratio = 500), and 0.05 grams of GeO2. The mixture was placed in a fume hood and allowed to evaporate until the mixture mass was 1.50 grams. 0.10 grams of 48% HF (2.5 mmol) was then added. The reaction vessel was then capped, sealed in a steel Parr autoclave, and heated with rotation (43 rpm) in a convection oven at 160°C for 6 days. The product was collected by centrifugation, washed with deionized water, and dried at 95°C.

[0054] Powder XRD analysis of the as-synthesized material showed that the material had a unique powder XRD pattern, which could not be matched with any known molecular sieve and was designated as pure as-synthesized SSZ-124 product.

[0055] SEM images of the product shown in Figures 1A and 1B suggest uniform crystalline fields.

[0056] A sample of the as-prepared product was calcined in a muffle furnace under air flow by heating the sample from room temperature to 540°C at a heating rate of 1°C / min and maintaining the temperature at 540°C for 6 hours. Figure 2 shows the powder XRD pattern of the as-calcined product.

[0057] The N2 adsorption measurements of the calcined product showed that the product was 204 m 2 / g BET surface area, and 0.0749 cm 3 / g micropore volume.

[0058] Example 2 A tared cup with a cap weight was filled with 7.5 mmol of N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene 2,5-diammonium dihydroxide was added along with the following solids: 0.40 grams of Tosoh 390HUA Y-zeolite, 0.40 grams of Zeolyst CBV600 Y-zeolite (H + -form, SiO2 / Al2O3 molar ratio = 60), and 0.15 grams of GeO2. The mixture was placed in a fume hood and allowed to evaporate until the mixture mass was 4.50 grams. 0.30 grams of 48% HF (7.5 mmol) was then added. The reaction vessel was then capped, sealed in a steel Parr autoclave, and heated with rotation (43 rpm) in a convection oven at 160°C for 6 days. The product was collected by centrifugation, washed with deionized water, and dried at 95°C.

[0059] The as-synthesized product was calcined in air at 540°C for 6 hours with a ramping rate of 1°C / min.

[0060] Powder XRD analysis of the as-prepared and calcined products showed that a pure SSZ-124 product was obtained.

[0061] Measurement by inductively coupled plasma atomic emission spectroscopy (ICP-AES) showed that the SiO2 / GeO2 molar ratio of the calcined product was 11.

[0062] The calcined product had a Bronsted acidity of 264.84 mmol / g as determined by n-propylamine temperature programmed desorption, indicating that aluminum sites were incorporated into the molecular sieve framework.

[0063] Example 3 Constraint Coefficient The constraint factor is a test for determining the shape-selective catalytic behavior of zeolites. This test compares the reaction rates for the cracking of n-hexane (n-C6) and its isomer, 3-methylpentane (3-MP), under competitive conditions (see V.J. Frillette et al., J. Catal. 1991, 67, 218-222).

[0064] The calcined molecular sieve from Example 2 was pelletized at 4 kpsi, crushed, and granulated to 20-40 mesh. A 0.6 g sample of the granulated material was calcined in air at 540°C for 4 hours and cooled in a desiccator to ensure dryness. 0.47 g of the material was then packed into a 1 / 4-inch stainless steel tube with alundum on both sides of the zeolite bed. The reactor tube was heated using an oven (Applied Test Systems, Inc.). Nitrogen was introduced into the reactor tube at 9.4 mL / min and atmospheric pressure. The reactor was heated to approximately 900°F (482°C), and a 50 / 50 feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 8 μL / min. The feed was delivered by an ISCO pump. Direct sampling to the GC was initiated 15 minutes after the feed was introduced.

[0065] Test data results after 136 minutes of operation (900°F) are shown in Table 4. [Table 4]

Claims

1. An aluminogermanosilicate molecular sieve having in its as-calcined form an X-ray powder diffraction pattern comprising the following lines: Table 1

2. In its as-produced form, an alumino germanosilicate molecular sieve having a powder x-ray containing the following lines: Table 2

3. 50 to 500 SiO ２ / Al ２ O ３ and 0.1 to 30 SiO ２ / GeO ２ 3. The aluminogermanosilicate molecular sieve according to claim 1, wherein the aluminogermanosilicate molecular sieve has a molar ratio of:

4. 100 to 250 SiO ２ / Al ２ O ３ and 0.5 to 15 SiO ２ / GeO ２ 3. The aluminogermanosilicate molecular sieve according to claim 1, wherein the aluminogermanosilicate molecular sieve has a molar ratio of:

5. In the pores, N ２ , N ２ , N ２ , N ５ , N ５ , N ５ 3. The aluminogermanosilicate molecular sieve of claim 2, comprising 2,3a,6a-octamethyloctahydropentalene 2,5-diammonium cations.

6. 1. A method for synthesizing an aluminogermanosilicate molecular sieve, comprising: （１） (a) an aluminosilicate molecular sieve having a FAU framework structure; (b) a germanium source; (c) N ２ , N ２ , N ２ , N ５ , N ５ , N ５ an organic structure-directing agent [Q] containing 3a,6a-octamethyloctahydropentalene 2,5-diammonium cation; (d) a source of fluoride ions [F], and (e) preparing a reaction mixture comprising water; (2) heating the reaction mixture to obtain an aluminogermanosilicate molecular sieve, wherein the aluminogermanosilicate molecular sieve has a framework structure different from that of the aluminosilicate molecular sieve.

7. 7. The method of claim 6, wherein the reaction mixture has the following composition in terms of molar ratios: Table 1-1

8. 7. The method of claim 6, wherein the reaction mixture has the following composition in terms of molar ratios: Table 1-2

9. 7. The method of claim 6, wherein the heating in (2) is carried out at a temperature in the range of 100°C to 200°C.

10. 7. The method of claim 6, wherein the heating in (2) is performed under autogenous pressure.

11. 7. The method of claim 6, wherein the heating in (2) is carried out for a period of 1 to 14 days.

12. 7. The method of claim 6, wherein the aluminosilicate molecular sieve is zeolite Y.

13. 7. The method of claim 6, wherein the germanium source is selected from the group consisting of germanium oxide, germanium nitrate, germanium alkoxide, and any combination thereof.

14. 7. The method of claim 6, wherein the structure directing agent [Q] is in its hydroxide form.

15. 7. The method of claim 6, wherein the fluoride ion source is selected from the group consisting of hydrogen fluoride, ammonium fluoride, ammonium bifluoride, and any combination thereof.

16. 7. The method of claim 6, further comprising calcining the aluminogermanosilicate molecular sieve obtained in (2).

17. 10. A process for converting organic compounds to conversion products, comprising contacting the organic compounds with the aluminogermanosilicate molecular sieve of claim 1.

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