Molecular sieve SSZ-124, synthesis and use thereof

Abstract

The present disclosure relates to aluminogermanosilicate molecular sieves named SSZ-124, processes for their preparation, and uses thereof.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 421,220, filed on November 1, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a new aluminogermanosilicate molecular sieve material named SSZ - 124, methods for its preparation, and its uses. Background Art

[0004] 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 a well - defined crystal structure determined by X - ray diffraction (XRD). Certain molecular sieves are ordered and produce specific recognizable XRD patterns. Inside certain molecular sieve materials, there may be a large number of cavities that are interconnected by many channels or pores. In a particular molecular sieve material, the sizes of these cavities and pores are uniform. Because the sizes of these pores can accommodate certain - sized adsorbed molecules while rejecting larger - sized adsorbed molecules, these materials have been called "molecular sieves" and are used in various industrial processes (e.g., cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization).

[0005] Molecular sieves applied to catalysis and adsorption include any of the naturally occurring or synthetic crystalline molecular sieves. Examples of these molecular sieves include macroporous 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 IUPAC Commission zeolite nomenclature rules. According to this classification, the framework - type zeolites with established structures and other crystalline microporous molecular sieves are assigned three - letter codes and are described in "Atlas of Zeolite Framework Types", edited by Ch. Baerlocher, L. B. McCusker, and D. H. Olson, Elsevier, 6th revised edition, 2007, which is hereby incorporated by reference. These zeolites and their isotypes are also described in the "Database of Zeolite Structures" of the IZA Structure Commission.

[0006] Although many different crystalline molecular sieves have been discovered, there is a continuing need for new molecular sieves having desirable properties for gas separation and drying, organic conversion reactions, and other applications. The new molecular sieves can include novel internal pore structures that provide enhanced selectivity in these processes. Summary of the Invention

[0007] This disclosure relates to aluminogermanosilicate molecular sieves, methods for their preparation, and their uses.

[0008] In one embodiment, this disclosure relates to a synthetic crystalline aluminogermanosilicate molecular sieve that, in its calcined form (e.g., where at least a portion of the structure-directing agent has been removed), has a powder X-ray diffraction pattern including at least the peaks listed in the following table:

[0009]

[0010] In a second embodiment, this disclosure relates to a synthetic crystalline aluminogermanosilicate molecular sieve that, in its as-synthesized form (e.g., where the structure-directing agent has not been removed), has a powder X-ray diffraction pattern including at least the peaks listed in the following table:

[0011]

[0012]

[0013] In a third embodiment, this disclosure relates to a method for preparing an aluminogermanosilicate molecular sieve, the method comprising: (1) preparing a reaction mixture comprising: (a) an aluminosilicate molecular sieve having a FAU framework structure, (b) a germanium source, (c) a structure-directing agent comprising N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene-2,5-diammonium cation, (d) a fluoride ion source, and (e) water; and (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.

[0014] In a fourth embodiment, this disclosure relates to a method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with an aluminogermanosilicate molecular sieve according to the first or second embodiment or an aluminogermanosilicate molecular sieve prepared by the method according to the third embodiment. Brief Description of the Drawings

[0015] Figure 1A and Figure 1BShows scanning electron microscope (SEM) images of the as-synthesized product of Example 1 at different magnifications.

[0016] Figure 2 Shows the powder X-ray diffraction (XRD) pattern of the calcined zeolite molecular sieve product of Example 1. Detailed implementation mode

[0017] The present disclosure relates to aluminogermanosilicate zeolites, methods for preparing the same, and uses thereof. The aluminogermanosilicate zeolite can be named SSZ-124 zeolite or SSZ-124 material.

[0018] Definition

[0019] The term "aluminosilicate" means a zeolite molecular sieve material having a framework structure composed of alumina and silica (i.e., repeating AlO4 and SiO4 tetrahedral units).

[0020] The term "aluminogermanosilicate" means a zeolite molecular sieve material having a framework structure composed of alumina, germanium oxide, and silica (i.e., repeating AlO4, GeO4, and SiO4 tetrahedral units).

[0021] The term "FAU" refers to the FAU-type topology or framework recognized by the Structure Commission of the International Zeolite Association (IZA), and the term "FAU zeolite" means an aluminosilicate in which the main crystalline phase is FAU.

[0022] The "as-synthesized" (or "as-received") aluminogermanosilicate zeolites of the present disclosure (i.e., before heat treatment or other treatment to remove the structure-directing agent from the pores) typically include a structure-directing agent in their pores, i.e., one of the components in the reaction mixture. The aluminogermanosilicate zeolites of the present disclosure in 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 "calcined" materials.

[0023] Synthesis of molecular sieve

[0024] Typically, the aluminogermanosilicate zeolites of the present disclosure can be synthesized by the following steps: (1) preparing a reaction mixture that contains (a) an aluminosilicate zeolite having a FAU framework structure, (b) a germanium source, (c) a structure-directing agent [Q] that contains N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5,3a,6a-octamethyloctahydropentalene-2,5-diammonium cation, (e) a fluoride ion source, and (f) water; and (2) 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.

[0025] The aluminogermanosilicate molecular sieve can be prepared from a reaction mixture having a composition in terms of molar ratios within the ranges shown in Table 1.

[0026] Table 1

[0027]

[0028]

[0029] The aluminosilicate molecular sieve having a FAU framework structure can be a single type of FAU molecular sieve or a mixture of two or more types of FAU molecular sieves. In certain embodiments, the FAU molecular sieve can be zeolite Y. The FAU molecular sieve can be two or more types of Y zeolites having different silica / alumina molar ratios. The FAU molecular sieve can be in the hydrogen form (H + form), ammonium form (NH4 + form) or a combination of these forms.

[0030] Suitable germanium sources include germanium oxide, germanium nitrate and alkoxygermaniums (e.g., tetraethoxygermanium).

[0031] Suitable fluoride ion sources include hydrogen fluoride (HF), ammonium fluoride (NH 4 F) and ammonium bifluoride (NH 4 HF 2 ), one or more of which.

[0032] The structure-directing agent [Q] contains the N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene-2,5-diammonium cation:

[0033]

[0034] The structure-directing agent [Q] can be in any suitable form, such as a halide, such as iodide or bromide, or as a hydroxide, for example in its hydroxide form.

[0035] The synthesis can be carried out with or without the addition of nucleating seeds. If nucleating seeds are added to the synthesis mixture, the seeds can have the same or a different structure from the aluminogermanosilicate molecular sieve or SSZ-124 material of the present disclosure, and can be present in an amount of 0.1 wt% to 10 wt%, preferably 0.5 wt% to 5 wt% based on 100 wt% of SiO 2 in the framework structure of the aluminosilicate FAU molecular sieve, based on 100 wt% of SiO 2 in the framework structure of the aluminosilicate FAU molecular sieve.

[0036] The reaction mixture can be prepared in any conceivable manner, and mixing by shaking is preferred, preferably by means of stirring. The reaction mixture can be prepared in batch, continuous or semi-continuous mode.

[0037] The reaction mixture can be in the form of a solution, a colloidal dispersion (colloidal sol), a gel or a paste, with a gel being preferred.

[0038] Then the reaction mixture is subjected to crystallization conditions suitable for forming the aluminogermanosilicate molecular sieve. Crystallization of the aluminogermanosilicate molecular sieve can be carried out under static or stirred conditions in a suitable reaction vessel (e.g., a Teflon-lined or stainless-steel autoclave placed in a convection oven maintained at an appropriate temperature).

[0039] Crystallization is typically 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 a higher temperature, the crystallization time can be reduced. For example, the crystallization conditions can 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.

[0040] Generally, the aluminogermanosilicate molecular sieve forms in solution and can be recovered by any well-known separation technique (e.g., decantation, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique and combinations thereof). The recovered solid can then be washed with deionized water or purified water and dried at an elevated temperature for several hours. The drying step can be carried out under vacuum or at atmospheric pressure.

[0041] In the drying step, after the crystallization step or after the washing step, water is removed from the aluminogermanosilicate molecular sieve. The conditions of the drying step are arbitrary, but an example is to dry the molecular sieve by allowing it to stand in an environment with a temperature not lower than 50 °C and not higher than 150 °C for at least two hours (e.g., 4 hours to 24 hours) after the crystallization step or after the washing step.

[0042] As a result of the crystallization process, the recovered synthetic zeolite molecular sieve product contains at least a portion of the structure directing agent used in the synthesis within its pores. Thus, the as-synthesized aluminogermanium silicate zeolite can be heat treated or otherwise treated to remove some or all of the structure directing agent incorporated into its pores during synthesis. Heat treatment of the as-synthesized aluminogermanium silicate zeolite (e.g., calcination) typically exposes 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. The heat treatment can be carried out at a temperature of 400 °C to 700 °C (e.g., 450 °C to 600 °C). The heat treatment can be carried out for at least 1 hour and generally not more than 20 hours (e.g., 2 hours to 10 hours, or 3 hours to 7 hours). Heating can first be carried out in a nitrogen atmosphere at up to 400 °C, and then the atmosphere can be switched to air at 400 °C to 700 °C.

[0043] Characterization of molecular sieve

[0044] The aluminogermanium silicate zeolite of the present disclosure can have a SiO 2 / Al 2 O 3 molar ratio of 50 or greater (e.g., 50 to 500, or 100 to 500, or 50 to 250, or 100 to 250).

[0045] The aluminogermanium silicate zeolite of the present disclosure can have a SiO 2 / GeO 2 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 2 / Al 2 O 3 and SiO 2 / GeO 2 molar ratios of the zeolite can be determined by conventional analysis.

[0046] The crystals of the aluminogermanium silicate zeolite can have a d50 crystal size of 5 mm or less (e.g., 0.5 mm to 5 mm).

[0047] The crystal size is based on individual crystals (including twins), but does not include agglomerates of crystals. The crystal size is the length of the longest diagonal of a three-dimensional crystal. Direct measurement of the crystal size can be carried out using microscopic methods such as SEM and transmission electron microscopy (TEM). For example, measurement by SEM involves examining the morphology of the material at high magnifications (usually 1000× to 100,000×). The SEM method can be carried out as follows: A representative portion of the molecular sieve powder is distributed in a suitable amount such that individual particles are reasonably uniformly dispersed throughout the field of view at magnifications of 1000× to 100,000×. From this population, a statistically significant sample of random individual crystals (e.g., 50 - 200) is examined, and the longest diagonal of the individual crystals is measured and recorded. Particles that are clearly large polycrystalline aggregates should not be included in the measurement results. Based on these measurement results, the d50 of the sample crystal size is calculated.

[0048] As-synthesized aluminogermanosilicate molecular sieves (e.g., as-prepared without heat treatment) have a characteristic powder XRD pattern that includes at least the lines listed in Table 2.

[0049] Table 2 Characteristic powder XRD peaks of as-synthesized SSZ-124

[0050]

[0051] Calcined aluminogermanosilicate molecular sieves (e.g., in which at least part of the structure-directing agent has been removed) have a characteristic powder XRD pattern that includes at least the peaks set forth in Table 3.

[0052] Table 3 Characteristic powder XRD peaks of calcined SSZ-124

[0053]

[0054] The powder X-ray diffraction pattern is determined by standard techniques. The radiation is copper K-α / doublet, and a scintillation counter spectrometer with a strip chart recorder is used. The peak heights I and their positions are read from the spectrometer chart in units of 2-θ (2θ), where θ is the Bragg angle. Based on these measured values, the relative intensity 100I / I 0 , where I 0 is the intensity of the strongest line or peak, and d is the interplanar spacing in angstroms corresponding to the recorded line. The relative intensity is based on the strongest line in the X-ray pattern, which is assigned a value of 100. The relative intensity is given in the symbols VS = very strong (greater than 60 to 100), S = strong (greater than 40 to 60), M = medium (greater than 20 to 40), W = weak (less than 20). When converted to the corresponding values of d-spacing using Bragg's law, the reported d-spacing values have a deviation determined based on the corresponding deviation of ±0.20 degrees 2-θ.

[0055] Minor variations in the diffraction pattern values in the tables or figures may occur due to, for example, the nature and extent of pore filling, framework composition, and changes in crystal size and shape. Despite these minor perturbations, the basic crystal structure of the as-synthesized and calcined materials remains substantially unchanged.

[0056] 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, which 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 in the alternative "substantially pure") means that the aluminogermanosilicate molecular sieve contains a lesser portion (less than 50 wt%), preferably less than 20 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%, and most preferably less than 1 wt% (e.g., less than 0.5 wt% or 0.1 wt%) of such impurities, and the weight percentage (wt%) value of such impurities is based on the combined weight of the impurities and the pure aluminogermanosilicate molecular sieve. The amount of impurities can be appropriately determined by powder XRD, rotational electron diffraction, and / or SEM / TEM (e.g., different crystal morphologies).

[0057] The aluminogermanosilicate molecular sieves described herein are substantially crystalline. As used herein, the term "crystalline" refers to the crystalline solid form of a material, including single-component or multi-component crystal forms (e.g., including solvates, hydrates, and co-crystals). Crystalline can mean having regularly repeating and / or ordered arrangements of molecules and having a distinguishable lattice. For example, the aluminogermanosilicate molecular sieve can have different water or solvent contents. Different lattices can be identified by solid-state characterization methods such as by XRD (e.g., powder XRD). Other characterization methods known to those of ordinary skill in the relevant art can further assist in identifying the crystalline form and in determining stability and solvent / water content. As used herein, the term "substantially crystalline" means that a sample of the material that is greater than 50 wt% by weight is crystalline and the remainder of the sample is in an amorphous form. In one or more aspects, a substantially crystalline sample has a crystallinity of at least 95% (e.g., 5% amorphous form), at least 96% (e.g., 4% amorphous form), at least 97% (e.g., 3% amorphous form), at least 98% (e.g., 2% amorphous form), at least 99% (e.g., 1% amorphous form), and 100% (e.g., 0% amorphous form).

[0058] Use of aluminogermanosilicate molecular sieve

[0059] The aluminogermanosilicate molecular sieve of the present disclosure (wherein some or all of the structure-directing agent has been removed) can be used as an adsorbent or a catalyst or as a support for a catalyst in a variety of hydrocarbon conversions (e.g., the conversion of an organic compound into a conversion product). Accordingly, the present disclosure thus relates to the use of the aluminogermanosilicate molecular sieve as described herein as an adsorbent or as a catalyst or as a support for a catalyst in hydrocarbon conversions. The present disclosure also relates to a method for converting an organic compound into a conversion product, the method comprising contacting the organic compound with the aluminogermanosilicate molecular sieve as described herein.

[0060] The aluminogermanosilicate molecular sieve of the present disclosure (wherein some or all of the structure-directing agent is removed) can be used as an adsorbent, such as for separating at least one component from a mixture of components in a gas phase or a liquid phase having different adsorption characteristics for the material. Thus, by contacting the mixture with the aluminogermanosilicate molecular sieve to selectively adsorb one component, at least one component can be partially or substantially completely separated from a mixture of components having different adsorption characteristics for the aluminogermanosilicate molecular sieve. For example, in a method for selectively separating one or more desired components of a feedstock from the remaining components of the feedstock, the feedstock can be contacted with an adsorbent comprising the aluminogermanosilicate molecular sieve of the present disclosure under effective adsorption conditions, thereby forming an adsorbed product and an effluent product. One or more of the desired components are recovered from the adsorbed product or the effluent product.

[0061] The aluminogermanosilicate molecular sieve of the present disclosure (wherein some or all of the structure-directing agent is removed) can also be used as a catalyst to catalyze a variety of organic compound conversion processes. Examples of chemical conversion methods effectively catalyzed by the aluminogermanosilicate molecular sieve described herein alone or in combination with one or more other catalytically active substances (including other crystalline catalysts) include those that require a catalyst having acid activity. Examples of organic conversion processes that can be catalyzed by the aluminogermanosilicate molecular sieve described herein include cracking, hydrocracking, isomerization, oligomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodewaxing, alkylation, transalkylation, dealkylation, disproportionation, hydrocracking of rings, dehydrogenation cyclization, conversion of methanol to olefins, deNO x applications and combinations thereof. The conversion of the hydrocarbon feed can be carried out in any convenient manner, such as in a fluidized bed, a moving bed or a fixed bed reactor, depending on the type of process desired.

[0062] The aluminogermanosilicate molecular sieve of the present disclosure can be formulated into a product composition by combination with other materials, such as binders and / or matrix materials that provide additional hardness to the final product. These other materials can be inert or catalytically active materials.

[0063] For example, it may be desirable to combine the aluminogermanosilicate molecular sieve of the present disclosure with another material that is tolerant of the temperatures and other conditions employed during use. Such materials include synthetic or naturally occurring zeolites and inorganic materials such as clays, silica, and / or metal oxides such as alumina and mixtures thereof. The metal oxides can be naturally occurring or in the form of a gelatinous precipitate or gel, including mixtures of silica and metal oxides. Combining the use of a crystal-active tolerant material with the aluminogermanosilicate molecular sieve of the present disclosure (i.e., in combination with it or present during the synthesis of the synthetic aluminogermanosilicate molecular sieve) tends to change the conversion rate and / or selectivity of the catalyst in certain organic conversion processes. Inactive tolerant materials are suitable as diluents to control the amount of conversion in a given process so that the product can be obtained in an economical and orderly manner without using other means to control the reaction rate. These materials can be incorporated into naturally occurring clays (such as bentonite and kaolin) to improve the crush strength of the product under commercial operating conditions. These inactive tolerant materials (i.e., clays, oxides, etc.) are used as binders for the catalyst. A catalyst with good crush strength is beneficial because it is desirable to prevent the catalyst from breaking into powdered material during commercial use.

[0064] Naturally occurring clays that can be used include montmorillonite and the kaolin family, which includes sub-bentonite and kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others, where the main mineral groups are halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in their as-mined, raw state or after being subjected to calcination, acid treatment, or chemical modification. Binders that can be used in combination with the aluminogermanosilicate molecular sieve of the present disclosure also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, yttria, gallia, zinc oxide, and mixtures thereof.

[0065] In addition to the above materials, the aluminogermanosilicate molecular sieve of the present disclosure can be combined with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylla, silica-titania, and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0066] These binder materials are resistant to the temperatures and other conditions (e.g., mechanical wear) encountered in various hydrocarbon conversion processes. Thus, the aluminogermanosilicate molecular sieves of the present disclosure can be used in the form of an extrudate containing a binder. They are typically agglomerated by forming pellets, spheres, or extrudates. Extrudates are generally formed by extruding the molecular sieve, optionally in the presence of a binder, and drying and calcining the resulting extrudate. Further treatments, such as steaming and / or ion exchange, can be carried out as needed. The molecular sieve can optionally be bound with a binder having a surface area of at least 100 m 2 / g (e.g., at least 200 m 2 / g, or at least 300 m 2 / g).

[0067] The relative proportions of the aluminogermanosilicate molecular sieve and the inorganic oxide matrix can vary over a wide range, with the aluminogermanosilicate molecular sieve content ranging from 1 wt% to 99 wt%, and more typically especially when the composite is prepared in the form of an extrudate, ranging from 2 wt% to 95 wt%, optionally 20 wt% to 90 wt% of the composite.

[0068] Examples

[0069] The following illustrative examples are intended to be non-limiting.

[0070] Example 1

[0071] To a capped and tared weighing cup, 2.5 millimoles of N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene-2,5-dihydroxydiammonium and the following solids were added: 0.27 grams of To soh 390HUAY-zeolite (H + -form, SiO 2 / Al 2 O 3 molar ratio = 500) and 0.05 grams of Ge O 2 . The mixture was placed in a fume hood and evaporated to a mass of 1.50 grams. Then, 0.10 grams of 48% HF (2.5 millimoles) was added. The reaction vessel was then capped and sealed inside a steel Parr autoclave and heated in a convection oven at 160 °C with rotation (43 rpm) for 6 days. The product was recovered by centrifugation, washed with deionized water, and dried at 95 °C.

[0072] Powder XRD analysis of the as-synthesized material showed that the material had a unique powder XRD pattern that did not match any known molecular sieve and was designated as a pure as-synthesized SSZ-124 product.

[0073] Figure 1A and Figure 1B SEM images of the products shown in

[0074] Samples of the as-prepared product were calcined in a muffle furnace under a stream of air by heating the sample from room temperature to 540 °C at a heating rate of 1 °C / min and holding at 540 °C for 6 hours. Figure 2 The powder XRD pattern of the calcined product is shown.

[0075] N 2 adsorption measurements of the calcined product showed that the product had a BET surface area of 204 m 2 / g and a micropore volume of 0.0749 cm 3 / g.

[0076] Example 2

[0077] 7.5 mmol of N 2 ,N 2 ,N 2 ,N 5 ,N 5 ,N 5 ,3a,6a-octamethyloctahydropentalene-2,5-dihydroxydiammonium and the following solids were added to a weighing cup that had been tared: 0.40 g of Tosoh 390HUA Y-zeolite, 0.40 g of Zeolyst CBV600Y-zeolite (H + -form, SiO 2 / Al 2 O 3 molar ratio = 60) and 0.15 g of GeO 2 . The mixture was placed in a fume hood and evaporated to a combined mass of 4.50 g. Then, 0.30 g of 48% HF (7.5 mmol) was added. The reaction vessel was then capped and sealed inside a steel Parr autoclave and heated in a convection oven at 160 °C with rotation (43 rpm) for 6 days. The product was recovered by centrifugation, washed with deionized water, and dried at 95 °C.

[0078] The as-synthesized product was calcined in air at a heating rate of 1 °C / min at 540 °C for 6 hours.

[0079] Powder XRD analysis of the as-prepared product and the calcined product showed that a pure SSZ-124 product was obtained.

[0080] Analysis by inductively coupled plasma atomic emission spectroscopy (ICP-AES) showed that the calcined product had a SiO 2 / GeO 2 molar ratio of 11.

[0081] As determined by temperature-programmed desorption of n-propylamine, the calcined product has a Bronsted acidity of 264.84 mmol / g acidity), indicating that the aluminum sites are incorporated into the framework of the molecular sieve.

[0082] Example 3

[0083] Constraint Index

[0084] The constraint index is a test for determining the shape-selective catalytic behavior in zeolites. It compares the reaction rates of 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).

[0085] The calcined molecular sieve of Example 2 was granulated at 4 kpsi, crushed and granulated to 20 - 40 mesh. A 0.6 g sample of the granular material was calcined in air at 540 °C for 4 hours and cooled in a desiccator to ensure dryness. Then, 0.47 g of the material was filled into a 1 / 4-inch stainless steel tube with alundum on both sides of the zeolite bed. The reactor tube was heated using a furnace (Applied Test Systems, Inc.). Nitrogen was introduced into the reactor tube at 9.4 mL / min and at 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 into the GC was started 15 minutes after the feed was introduced.

[0086] The test data results after 136 minutes of continuous operation (900 °F) are presented in Table 4.

[0087] Table 4 Constraint Index Test

[0088] n-C6 conversion rate [%] 8.2 3-MP conversion rate [%] 1.3 Feed conversion rate [%] 4.7 Constraint index (excluding 3-MP) 6.45 Constraint index (including 3-MP) 6.45

Claims

1. An aluminogermanosilicate molecular sieve which, in its calcined form, has a powder X-ray diffraction pattern comprising the following lines:

2. An aluminogermanosilicate molecular sieve which, in its as-synthesized form, has a powder X-ray comprising the following lines:

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

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

5. The aluminogermanosilicate molecular sieve according to claim 2, which contains N in its pores 2 , N 2 , N 2 , N 5 , N 5 , N 5 , 3a,6a-octamethyloctahydropentalene-2,5-diammonium cation.

6. A method for synthesizing an aluminogermanosilicate molecular sieve, the method comprising: (1) preparing a reaction mixture comprising: (a) an aluminosilicate molecular sieve having a FAU framework structure, (b) a germanium source, (c) An organic structure-directing agent [Q] comprising N 2 , N 2 , N 2 , N 5 , N 5 , N 5 , the 3a,6a-octamethyloctahydropentalene-2,5-diammonium cation, (d) a fluoride ion source [F], and (e) water; and (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. The method according to claim 6, wherein the reaction mixture has the following composition in terms of molar ratios:

8. The method according to claim 6, wherein the reaction mixture has the following composition in terms of molar ratios:

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

10. The method according to claim 6, wherein the heating in (2) is carried out under autogenous pressure.

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

12. The method according to claim 6, wherein the aluminosilicate molecular sieve is zeolite Y.

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

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

15. The method according to 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. The method according to claim 6, further comprising calcining the aluminogermanosilicate molecular sieve obtained in (2).

17. A method for converting an organic compound into a conversion product, comprising contacting the organic compound with the aluminogermanosilicate molecular sieve according to claim 1.

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