SCM-41 molecular sieve, its preparation method, and its use

Abstract

This invention discloses a novel silicon-germanium molecular sieve, SCM-41, a method for producing the same, and its use. The SCM-41 molecular sieve has a unique X-ray diffraction pattern and shows promising prospects for application in the adsorption separation and catalytic conversion of organic compounds.

Description

Detailed description of the invention

[0001] [Technical Field] This application belongs to the field of molecular sieves, and more particularly to the silicon-germanium molecular sieve SCM-41, a method for producing the same, and its use.

[0002] [Background technology] Molecular sieves are an important class of microporous crystalline materials possessing regularly arranged molecular-scale channel structures, tunable chemical compositions, relatively strong acidity, and high hydrothermal stability. Currently, molecular sieves are widely used in fields such as catalysis, adsorption, and ion exchange. The superior performance of molecular sieves largely depends on their framework structure. Therefore, the synthesis of molecular sieves with specific framework structures has always been one of the most important research objectives in the field of molecular sieves.

[0003] To date, more than 250 types of molecular sieves with novel framework structures have been discovered. The framework structure of molecular sieves is typically formed by coordination tetrahedra (TO4) connected via shared vertices (generally oxygen atoms). Among these, the tetrahedra in the framework structure of zeolite molecular sieves are the SiO4 tetrahedron and the AlO4 tetrahedron. These two types of tetrahedra in zeolite molecular sieves can be replaced by other types of tetrahedra to form molecular sieves or molecular sieve-like materials with different framework structures. For example, the AlO4 tetrahedron can be replaced by the GaO4 or ZnO4 tetrahedron, which together with the SiO4 tetrahedron constitute the framework of a heteroatom molecular sieve, while Ge has coordination properties similar to Si and can also form tetrahedral coordination structures. The bonding of GeO4 and SiO4 can form numerous novel germanium-containing molecular sieves or molecular sieve-like structures.

[0004] To date, no material having the same X-ray diffraction crystal structure as the SCM-41 molecular sieve disclosed in this application has been recognized.

[0005] 〔overview〕 The object of this application is to provide a novel silicon-germanium molecular sieve SCM-41, a method for producing the same, and its use. The molecular sieve has a novel framework structure and a unique X-ray diffraction pattern and can be used as an adsorbent, catalyst, or its active ingredient.

[0006] To achieve the above objective, in one embodiment, this application provides a silicon-germanium molecular sieve having an X-ray diffraction pattern exhibiting the X-ray diffraction peaks shown in the following table: [Table 1] .

[0007] Preferably, the silicon-germanium molecular sieve exhibits the X-ray diffraction peaks shown in the following table: [Table 2] .

[0008] Preferably, the molecular sieve further contains additional element X selected from boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, indium, or combinations thereof.

[0009] In another embodiment, a method for producing the silicon-germanium molecular sieve of the present application is provided, comprising the steps of: mixing a silicon source, a germanium source, a fluorine source, an organic template Q, water, and an optional additional element X source to obtain the silicon-germanium molecular sieve; subjecting to a crystallization reaction; and optionally calcining, wherein the organic template Q comprises 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol or consists of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol].

[0010] In yet another embodiment, a molecular sieve composition is provided, which comprises the silicon-germanium molecular sieve and active ingredients and / or binders of the present application.

[0011] In yet another embodiment, the use of the molecular sieve or molecular sieve composition of this application as an adsorbent or catalyst is provided.

[0012] The silicon-germanium molecular sieve SCM-41 of this application has a completely novel framework structure not obtained in the prior art. The SCM-41 molecular sieve has a regularly sized channel structure, relatively strong acidity, ion exchange properties, and high thermal stability, showing good potential for application in the adsorption separation and catalytic transformation of organic compounds.

[0013] The method for producing SCM-41 molecular sieves described in this application has a simple synthesis process, good operability, a wide range of synthesis possibilities, and is easily disseminated.

[0014] [Brief explanation of the drawing]

[0015] Figure 1 shows a schematic diagram (a) of the natural tile set in the framework of the SCM-41 molecular sieve obtained in Example 1, and its tiling structure (b);

[0016] Figure 2 shows a schematic diagram (a) and its tiling structure (b) of another set of natural tiles in the framework of the SCM-41 molecular sieve obtained in Example 1;

[0017] Figure 3 shows projections from different directions of one framework structure of the SCM-41 molecular sieve obtained in Example 1;

[0018] Figure 4 shows projections from different directions of another framework structure of the SCM-41 molecular sieve obtained in Example 1;

[0019] Figures 5A and 5B show the X-ray diffraction (XRD) patterns of the SCM-41 molecular sieve obtained in Example 1 and the molecular sieve immediately after synthesis, respectively;

[0020] Figure 6 shows scanning electron microscope (SEM) images of the SCM-41 molecular sieve obtained in Example 1;

[0021] Figure 7 shows the nitrogen adsorption-desorption isotherm of the SCM-41 molecular sieve obtained in Example 1;

[0022] Figures 8A and 8B show the XRD patterns of the SCM-41 molecular sieve obtained in Example 2 and the molecular sieve immediately after synthesis, respectively;

[0023] Figure 9 shows an SEM image of the SCM-41 molecular sieve obtained in Example 2;

[0024] Figure 10 shows the nitrogen adsorption-desorption isotherm of the SCM-41 molecular sieve obtained in Example 2; and

[0025] Figure 11 shows the XRD pattern of the BEC molecular sieve obtained in Comparative Example 1.

[0026] [Detailed explanation] Specific embodiments of this application are described in detail below. The specific embodiments described herein are for illustrative and illustrative purposes only and should be understood as not intended to limit this application.

[0027] Any specific numerical value disclosed herein (including the endpoints of a numerical range) should be understood not to be limited to its exact value, but to include all possible values ​​close to its exact value, for example, within ±5% of the exact value. Furthermore, with respect to a disclosed numerical range, one or more new numerical ranges can be arbitrarily formed by combining endpoint values, endpoint values ​​with values ​​at specific points within the range, and values ​​at each specific point. These new numerical ranges should also be deemed expressly disclosed herein.

[0028] Unless otherwise specified, terms used herein have the same meaning as those generally understood by those skilled in the art. In the event of any discrepancy between a term defined herein and its definition in this specification and the general understanding of those skilled in the art, the definition herein shall prevail.

[0029] In the context of this specification, the term “specific surface area” refers to the total surface area per unit mass of a sample, which includes both internal and external surface area. Non-porous samples, such as Portland cement and certain clay mineral powders, have only external surface area; porous samples, such as asbestos fibers, diatomite, and molecular sieves, have both external and internal surface area. In porous samples, the surface area of ​​pores with a diameter of less than 2 nm is the internal surface area. The surface area obtained by subtracting the internal surface area is called the external surface area. The external surface area per unit mass of a sample is the external specific surface area.

[0030] In the context of this specification, the term "SiO2 / GeO2 molar ratio" refers to the molar ratio of silicon, calculated as SiO2, to germanium, calculated as GeO2, in a molecular sieve.

[0031] In the context of this specification, the term "calculated as an oxide" means that the corresponding element has been calculated in the form of an oxide at the highest valence in which it can stably exist. For example, the expression "calculated as an oxide" for silicon means that it has been calculated as SiO2, for germanium as GeO2, for aluminum as Al2O3, for titanium as TiO2, for boron as B2O3, for zirconium as ZrO2, for tin as SnO2, and for iron as Fe2O3.

[0032] In the context of this specification, the terms “immediately after synthesis,” “immediately after synthesis,” or “immediately after synthesis molecular sieve” refer to the state of the molecular sieve after the synthesis process is complete and before any post-processing steps (e.g., calcination) begin. A specific example of the immediately after synthesis state may be the state directly shown after the synthesis process is complete. With this in mind, the immediately after synthesis state may contain water and / or organic matter (especially organic templates).

[0033] In the context of this specification, the terms “calcined,” “calcined state,” or “calcined molecular sieve” refer to the state of a molecular sieve after calcination. A specific example of a calcined state is the state shown after further calcining a molecular sieve immediately after synthesis to remove any organic matter (especially organic templates) and water that may be present in its pores.

[0034] In the context of this specification, in XRD data of molecular sieves, symbols such as vw, w, m, s, and vs represent the relative intensity I / I0 of diffraction peaks at the corresponding angle of 2θ with respect to the strongest diffraction peak (i.e., the diffraction peak with the greatest intensity), calculated based on the diffraction peak intensity (measured at peak height). Here, I represents the peak intensity of the corresponding diffraction peak, I0 represents the peak intensity of the strongest diffraction peak, vw represents very weak, w represents weak, m represents moderate, s represents strong, and vs represents very strong. This notation is well known to those skilled in the art. Generally, vw represents less than 5, w represents 5 to 20 (excluding 20), m represents 20 to 40 (excluding 40), s represents 40 to 70 (excluding 70), and vs represents 70 or greater.

[0035] According to this application, the interplanar spacing (d-spacing) of each diffraction peak in the XRD pattern of a molecular sieve can be calculated from the 2θ value of the diffraction peak using Bragg's law: λ = 2d sinθ (where λ is the wavelength of the incident wave, λ = 1.54 Å, d is the interplanar spacing, and θ is the angle between the incident light and the scattering plane).

[0036] In the context of this specification, the term “pore volume” refers to the volume of pores per unit mass of the molecular sieve. The term “total pore volume” refers to the volume of all pores per unit mass of the molecular sieve (generally including only pores with a diameter of less than 50 nm). The term “micropore volume” refers to the volume of all micropores per unit mass of the molecular sieve (generally referring to pores with a diameter of less than 2 nm).

[0037] In this application, the pore structure parameters of the molecular sieve material, such as total pore volume, micropore volume, and specific surface area, are obtained by performing nitrogen physicoadsorption-desorption isotherm measurements of the molecular sieve using a physicoadsorption apparatus, and then calculating them based on the BET (Brunauer-Emmett-Teller) method and the t-plot method. The total pore volume is considered to be the pore volume corresponding to a relative pressure P / P0 = 0.99. Specific test and calculation methods are well known to those skilled in the art.

[0038] In this application, the content of Si, Ge, and element X in the molecular sieve is determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the content of F, organic template, and water is determined by thermogravimetric analysis.

[0039] Except as expressly stated in this application, any matters or items not mentioned are directly applicable without modification to those known in the art. Furthermore, any embodiment described herein may be freely combined with one or more other embodiments described herein, and unless such combination is clearly unreasonable to a person skilled in the art, the resulting technical solution or technical idea shall be considered part of the original disclosure or original record of this application and shall not be considered novel content not disclosed or foreseen herein.

[0040] All patent documents and non-patent documents, including but not limited to textbooks and academic articles, cited herein are incorporated herein by reference in their entirety.

[0041] As described above, a first aspect of this application provides a silicon-germanium molecular sieve having an X-ray diffraction pattern exhibiting the X-ray diffraction peaks shown in the following table: [Table 3] .

[0042] In one preferred embodiment, the silicon-germanium molecular sieve exhibits the X-ray diffraction peaks shown in the table below: [Table 4] In this preferred embodiment, the silicon-germanium molecular sieve is a calcined silicon-germanium molecular sieve, also referred to in this application as an SCM-41 molecular sieve.

[0043] In a more preferred embodiment, the X-ray diffraction pattern of the SCM-41 molecular sieve further shows one or more X-ray diffraction peaks, as shown in the table below: [Table 5] .

[0044] In a more preferred embodiment, the X-ray diffraction pattern of the SCM-41 molecular sieve further shows one or more X-ray diffraction peaks, as shown in the table below: [Table 6] .

[0045] In a more preferred embodiment, the X-ray diffraction pattern of the SCM-41 molecular sieve exhibits the relative intensity characteristics of the diffraction peaks shown in the table below: [Table 7] .

[0046] In an even more preferred embodiment, the X-ray diffraction pattern of the SCM-41 molecular sieve further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: [Table 8] .

[0047] In an even more preferred embodiment, the X-ray diffraction pattern of the SCM-41 molecular sieve further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: [Table 9] .

[0048] In a more preferred embodiment, the SCM-41 molecular sieve has a framework topology including natural tiles of [4 6 , [4 4 .6 2 , [4 2 .5 4 , [4 2 .5 4 .6 2 , [4 7 .5 6 .6 9 .10 4 as shown in Figure 1a.

[0049] In an even more preferred embodiment, the SCM-41 molecular sieve has a framework topology with a minimum repeating unit that may be composed of two [4 6 , two [4 4 .6 2 , two [4 2 .5 4 , one [4 2 .5 4 .6 2 , two [4 7 .5 6 .6 9 .10 4 of natural tiles as shown in Figure 1b.

[0050] In another more preferred embodiment, the SCM-41 molecular sieve is as shown in Figure 2a, [4 6 ], [4 4 .6 2 ], [4 2 .5 4 ], [4 2 .6 4 ], [4 14 .5 8 .6 16 .10 8 It has a framework topology that includes natural tiles.

[0051] In a more specific embodiment, the SCM-41 molecular sieve is made up of two [4] as shown in Figure 2b. 6 ], two [4 4 .6 2 ], two [4 2 .5 4 ], one [4 2 .6 4 ], two [4 14 .5 8 .6 16 .10 8 It has a framework topology that has the smallest repeating unit composed of natural tiles.

[0052] In a more preferred embodiment, the SCM-41 molecular sieve has intersecting linear channels having 10-membered ring openings along the

[0010] and

[0110] directions of the crystal.

[0053] In a further preferred embodiment, the linear channel having the opening of the 10-membered ring of the SCM-41 molecular sieve has an elliptical planar projection. For example, the major axis of the ellipse may be 6.0-7.0 Å, preferably 6.1-6.9 Å, more preferably 6.2-6.8 Å, and / or the minor axis of the ellipse may be 4.4-5.4 Å, preferably 4.5-5.3 Å, more preferably 4.6-5.2 Å.

[0054] In a more preferred embodiment, the SCM-41 molecular sieve belongs to the monoclinic crystal system.

[0055] In a more preferred embodiment, the SCM-41 molecular sieve has a unit cell parameter of a = 17.0 to 19.0 Å, preferably a = 17.2 to 18.8 Å, and more preferably a = 17.4 to 18.6 Å.

[0056] In a more preferred embodiment, the SCM-41 molecular sieve has a unit cell parameter of b = 12.6 to 14.6 Å, preferably b = 12.8 to 14.4 Å, and more preferably b = 13.0 to 14.2 Å.

[0057] In a more preferred embodiment, the SCM-41 molecular sieve has a unit cell parameter of c=21.2~23.2 Å, preferably c=21.4~23.0 Å, and more preferably c=21.6~22.8 Å.

[0058] In a more preferred embodiment, the SCM-41 molecular sieve has unit cell parameters of α=90° and γ=90°.

[0059] In a more preferred embodiment, the SCM-41 molecular sieve has a unit cell parameter of β=96~106°, preferably β=97~105°, and more preferably β=98~104°.

[0060] In a more preferred embodiment, the crystals of the SCM-41 molecular sieve have a plate-like morphology.

[0061] In a more preferred embodiment, the molar ratio of silicon calculated as SiO2 to germanium calculated as GeO2 in the SCM-41 molecular sieve, which is also referred herein as the silicon-germanium molar ratio or SiO2 / GeO2 molar ratio, is (0.25-25):1, preferably (0.5-20):1, more preferably (1-15):1, and even more preferably (1.5-10):1. Specific examples include SiO2 / GeO2 molar ratios of 0.25:1, 0.5:1, 1:1, 1.5:1, 2:1, 5:1, 10:1, 15:1, 20:1, 25:1, or any value in between.

[0062] In a more preferred embodiment, the SCM-41 molecular sieve is of the formula "SiO 2· It has a schematic chemical composition represented as "1 / n GeO2", where n represents the silicon-germanium molar ratio of the molecular sieve, and is 0.25 ≤ n ≤ 25, preferably 0.5 ≤ n ≤ 20, more preferably 1 ≤ n ≤ 15, and particularly preferably 1.5 ≤ n ≤ 10. For example, n may be 0.25, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, or any value in between. Those skilled in the art will understand that molecular sieves may occasionally contain a certain amount of water (especially immediately after synthesis), but the presence or absence of this water does not substantially affect the XRD pattern of the molecular sieve. Therefore, the water content is not limited in this application. Considering this, the schematic chemical composition shown above in this application represents the anhydrous chemical composition of this molecular sieve. Furthermore, it is clear that this schematic chemical composition represents the chemical composition of the framework of this SCM-41 molecular sieve.

[0063] In a further preferred embodiment, the SCM-41 molecular sieve may further contain additional elements X, which are selected from boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, indium, or a combination thereof, and are preferably selected from aluminum and titanium. Preferably, at least a portion of the additional elements are present in the form of oxides.

[0064] In a more preferred embodiment, when calculated based on the molar ratio of elements, the ratio of the total molar content of Si and Ge to the total molar content of all additional elements X in the molecular sieve is 5 or greater, preferably 10 or greater, and more preferably 10 to 100. As a specific example, when calculated based on the moles of elements, the ratio of the total molar content of Si and Ge to the total molar content of all additional elements X in the molecular sieve may be 5, 10, 20, 40, 60, 80, 100, 150, 200, or any value in between.

[0065] In a more preferred embodiment, in the SCM-41 molecular sieve, the silicon and germanium of the framework are partially substituted with an additional element X, the substitution rate not exceeding 20%. Here, the "substitution rate" is dimensionless and is calculated using moles according to the following formula: Substitution rate=X / (Si+Ge)×100%.

[0066] Particularly preferably, the additional element X substituting silicon and germanium is selected from boron, aluminum, tin, zirconium, titanium, or a combination thereof, and more preferably from aluminum and titanium.

[0067] In a more preferred embodiment, the SCM-41 molecular sieve is 250-1000 m 2 / g, preferably 300-800m 2 It has a specific surface area of ​​ / g (BET method).

[0068] In a more preferred embodiment, the SCM-41 molecular sieve is 0.1-0.4 cm 3 / g, preferably 0.12-0.35cm 3 It has a micropore volume of / g (t-plot method).

[0069] In other preferred embodiments, the silicon-germanium molecular sieve may be a silicon-germanium molecular sieve immediately after synthesis, with the formula "kF·mQ·SiO2·1 / nGeO2·pH2O" or "kF·mQ·SiO2·1 / nGeO2·qXO" y / 2 It has a schematic chemical composition represented by "pH2O", where Q is an organic template, X represents an element selected from boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, indium, or a combination thereof, preferably an element selected from aluminum and titanium, and y is the valence of element X, in the range of 1 to 7. Here, 0.25≦n≦25, preferably 0.5≦n≦20, more preferably 1≦n≦15, and especially preferably 1.5≦n≦10; 0.05≦k≦1.0, preferably 0.05≦k≦0.5, more preferably 0.1≦k≦0.5, and particularly preferably 0.1≦k≦0.4; 0.01 ≤ m ≤ 1.0, preferably 0.02 ≤ m ≤ 0.5, more preferably 0.05 ≤ m ≤ 0.5, and particularly preferably 0.05 ≤ m ≤ 0.3; 0.005≦p≦0.5, preferably 0.01≦p≦0.4, more preferably 0.01≦p≦0.3, and particularly preferably 0.02≦p≦0.2; 0≦q≦(1+1 / n) / 5, preferably 0≦q≦(1+1 / n) / 10, and more preferably (1+1 / n) / 100≦q≦(1+1 / n) / 10.

[0070] In this application, the organic template Q contains or consists of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol. The structural formula of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, also known as 1-[di(3-dimethylaminopropyl)amino]-2-propanol, or 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol], is as follows: [ka] .

[0071] In a more preferred embodiment, the X-ray diffraction pattern of the silicon-germanium molecular sieve immediately after synthesis shows one or more X-ray diffraction peaks, as shown in the table below: [Table 10] .

[0072] In a more preferred embodiment, the X-ray diffraction pattern of the silicon-germanium molecular sieve immediately after synthesis shows one or more X-ray diffraction peaks, as shown in the table below: [Table 11] .

[0073] In a more preferred embodiment, the X-ray diffraction pattern of the silicon-germanium molecular sieve immediately after synthesis exhibits the relative intensity characteristics of the diffraction peaks, as shown in the table below: [Table 12] .

[0074] In a more preferred embodiment, the X-ray diffraction pattern of the silicon-germanium molecular sieve immediately after synthesis further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: [Table 13] .

[0075] In a particularly preferred embodiment, the X-ray diffraction pattern of the silicon-germanium molecular sieve immediately after synthesis further exhibits the relative intensity characteristics of the diffraction peaks shown in any one or more rows of the table below: [Table 14] .

[0076] Those skilled in the art will understand that molecular sieves immediately after synthesis generally contain organic matter (especially organic templates) and substances that fill their channels, such as water. Therefore, the SCM-41 molecular sieve of this application, immediately after synthesis, has the formula "kF·mQ·SiO2·1 / nGeO2·pH2O" or "kF·mQ·SiO2·1 / nGeO2·qXO y / 2 It may have a schematic chemical composition represented by "pH2O". Clearly, an SCM-41 molecular sieve can be obtained by calcining a molecular sieve immediately after synthesis having the above schematic chemical composition, and removing at least a portion of the organic template and water (if present) in its channels.

[0077] According to this application, firing can be carried out by any conventionally known method. For example, the firing temperature is generally 300°C to 750°C, preferably 400°C to 600°C, and the firing time is generally 1 hour to 10 hours, preferably 3 hours to 6 hours. Furthermore, firing is generally carried out in an oxygen-containing atmosphere, for example, in air or an oxygen atmosphere.

[0078] In a second embodiment, a method for producing a silicon-germanium molecular sieve of the present application is provided, comprising the steps of: mixing a silicon source, a germanium source, a fluorine source, an organic template Q, water, and an optional additional element X source to obtain a silicon-germanium molecular sieve; subjecting to a crystallization reaction; and optionally calcining, wherein the organic template Q comprises 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol or consists of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol].

[0079] Those skilled in the art will understand that, in the method of this application, if calcination is not performed after the crystallization reaction, a silicon-germanium molecular sieve immediately after synthesis, as described in the first aspect of this application, is obtained, whereas if calcination is performed after the crystallization reaction, an SCM-41 molecular sieve, as described in the first aspect of this application, is obtained.

[0080] In this application, there are no strict limitations on the silicon source, and various silicon sources conventionally used in the fabrication of molecular sieves can be employed. In preferred embodiments, the silicon source is selected from water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomite, zeolite molecular sieves, tetraethyl orthosilicate, or a combination thereof, and more preferably from silica sol, fumed silica, tetraethyl tetraorthosilicate, or a combination thereof. These silicon sources can be used individually or in combinations of desired ratios.

[0081] In this application, there are no strict limitations on the germanium source, and various germanium sources conventionally used in the fabrication of silicon-germanium molecular sieves can be employed. In a preferred embodiment, the germanium source is selected from germanium oxide, germanium nitrate, tetraalkoxygermanium, or a combination thereof.

[0082] In this application, there are no strict limitations on the fluorine source, and various conventionally used water-soluble fluorides or aqueous solutions thereof can be employed. In preferred embodiments, the fluorine source is selected from hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride, or a combination thereof, and is preferably selected from hydrofluoric acid and ammonium fluoride.

[0083] According to this application, if it is necessary to include an additional element X in the silicon-germanium molecular sieve, for example, if this additional element X is used to replace some of the silicon and germanium in the framework of the molecular sieve, the source of the additional element X is further included in the raw materials for making the molecular sieve. In a preferred embodiment, the source of the additional element X is selected from a boron source, an aluminum source, a gallium source, a titanium source, a zirconium source, a hafnium source, a tin source, a zinc source, an iron source, a chromium source, an indium source, or a combination thereof; preferably, it is selected from a boron oxide source, an aluminum oxide source, a gallium oxide source, a titanium oxide source, a zirconium oxide source, a hafnium oxide source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, an indium oxide source, or a combination thereof. For example, aluminum oxide sources include, but are not limited to, aluminum hydroxide, sodium aluminate, aluminum salts, kaolin, and montmorillonite, or combinations thereof; boron oxide sources include, but are not limited to, boron oxide, borax, sodium metaborate, and boric acid, or combinations thereof; tin oxide sources include, but are not limited to, tin(IV) chloride, tin(II) chloride, alkyltin, alkoxytin, and organotin esters, or combinations thereof. Zirconium oxide sources include, but are not limited to, zirconium salts (e.g., zirconium nitrate, zirconium sulfate), alkylzirconium, alkoxyzirconium, and organozirconium esters, or combinations thereof. Titanium oxide sources include, but are not limited to, tetraalkyl titanates (e.g., tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra-n-butyl titanate), titanium tetrachloride, hexafluorotitanium acid, titanium sulfate, and one or more of their hydrolysis products.Gallium oxide sources include, but are not limited to, gallium nitrate, gallium oxide, gallium halides (e.g., gallium chloride, gallium bromide), gallium sulfate, gallium isopropoxide, gallium acetate, ethoxygallium, or combinations thereof; hafnium oxide sources include, but are not limited to, hafnium oxide, hafnium halides (e.g., hafnium chloride, hafnium bromide), hafnium sulfate, hafnium tert-butoxide, hafnium oxychloride, ethoxyhafnium, or combinations thereof; zinc oxide sources include, but are not limited to, zinc oxide, zinc halides (e.g., zinc chloride), This includes zinc acetate, basic zinc carbonate, zinc sulfate, zinc nitrate, zinc lactate, zinc gluconate, or combinations thereof; iron oxide sources include, but are not limited to, iron sulfate, iron nitrate, iron halides (e.g., iron chloride), ferrocene, iron citrate, or combinations thereof; chromium oxide sources include, but are not limited to, chromium(III) oxide, chromium chloride, chromium nitrate, chromium acetate, potassium chromium sulfate, or combinations thereof; and indium oxide sources include, but are not limited to, indium oxide, indium sulfate, indium halides (e.g., indium trichloride), indium acetate, or combinations thereof.

[0084] In a preferred embodiment, the molar ratio of the amounts of organic template Q, silicon source (calculated as SiO2), germanium source (calculated as GeO2), fluorine source (calculated as F), and water is (0.15~4):(0.2~0.97):(0.03~0.8):(0.2~4):(0.5~30), preferably (0.15~4):(0.2~0.9615):(0.0385~0.8):(0.2~4):(0.5~30), and more preferably (0 The ratios are 0.25~3.5):(0.3~0.96):(0.04~0.7):(0.35~3.5):(1~25), more preferably (0.3~2.5):(0.5~0.94):(0.06~0.5):(0.4~2.5):(2~20), and even more preferably (0.35~1.5):(0.6~0.91):(0.09~0.4):(0.45~2):(3~15), where the total molar amount of silicon source and germanium source is 1 part.

[0085] In a preferred embodiment, the ratio of the total molar amount of the additional element X source (calculated as element X) to the total molar amount of the silicon source (calculated as SiO2) and germanium source (calculated as GeO2) is (0 to 0.2):1, preferably (0 to 0.1):1, and more preferably (0.01 to 0.01):1.

[0086] In preferred embodiments, the crystallization reaction is carried out at 100-200°C for 24-360 hours, preferably at 110-190°C for 48-300 hours, and more preferably at 120-180°C for 72-240 hours. According to this application, the crystallization reaction can be carried out by any method conventionally known in the art. For example, it may include the step of mixing a silicon source, a germanium source, a fluorine source, an organic template Q, water, and optionally an additional element X source in predetermined proportions, and subjecting the resulting mixture to hydrothermal crystallization under crystallization conditions. Optionally, crystallization may also be carried out with stirring as needed.

[0087] According to this application, in a method for producing molecular sieves, after the crystallization reaction is completed, the resulting molecular sieves can be separated from the obtained reaction mixture by any conventionally known separation method, thereby obtaining silicon-germanium molecular sieves immediately after synthesis. Examples of separation methods include filtration, washing, and drying of the obtained reaction mixture. According to this application, filtration, washing, and drying can be carried out by any conventionally known method in the art. Specifically, as filtration, for example, the obtained reaction mixture can be simply filtered by suction. As washing, for example, washing with deionized water can be carried out. The drying temperature can be, for example, 40 to 250°C, preferably 60 to 150°C. The drying time can be, for example, 8 to 30 hours, preferably 10 to 20 hours. This drying can be carried out under atmospheric pressure or under reduced pressure.

[0088] According to this application, in a method for producing molecular sieves, if necessary, a molecular sieve obtained from a crystallization reaction, for example, a silicon-germanium molecular sieve immediately after synthesis, is calcined to remove any organic template and at least some of the moisture present (if any), thereby obtaining a calcined molecular sieve, i.e., the silicon-germanium molecular sieve SCM-41 of this application. Calcination can be carried out by any method conventionally known in the art. For example, the calcination temperature is generally 300 to 800°C, preferably 400 to 650°C, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In a preferred embodiment, calcination is carried out at 300 to 750°C for 1 to 10 hours, more preferably at 400 to 600°C for 3 to 6 hours. Furthermore, calcination is generally carried out in an oxygen-containing atmosphere, for example, in air or an oxygen atmosphere.

[0089] According to this application, silicon-germanium molecular sieves SCM-41 or silicon-germanium molecular sieves immediately after synthesis can be presented in any physical form, such as powder, granules, or molded articles (e.g., strips, trefoils, etc.). These physical forms can be obtained by any method conventionally known in the art and are not particularly limited.

[0090] In a third aspect of this application, the application provides a silicon-germanium molecular sieve, such as a silicon-germanium molecular sieve and / or SCM-41 molecular sieve immediately after synthesis, as well as a molecular sieve composition comprising an active material and / or a binder, as described in the first aspect of this application.

[0091] According to this application, SCM-41 molecular sieves or silicon-germanium molecular sieves immediately after synthesis can be combined with other materials to obtain molecular sieve compositions. Examples of other materials include active materials and inactive materials. Examples of active materials include synthetic zeolites and natural zeolites. Examples of inactive materials (generally referred to as binders) include clay, white clay, silica gel, and alumina. These other materials can be used individually or in any combination. The amounts of other materials are not particularly limited and can directly refer to conventional amounts in the art.

[0092] In a fourth aspect, the use of silicon-germanium molecular sieves, such as silicon-germanium molecular sieves and / or SCM-41 molecular sieves immediately after synthesis, according to the first aspect of this application, or molecular sieve compositions according to the third aspect, as adsorbents or catalysts is provided.

[0093] According to this application, SCM-41 molecular sieves, silicon-germanium molecular sieves immediately after synthesis, or molecular sieve compositions can be used as adsorbents to separate at least one component from a mixture of multiple components in the gas phase or liquid phase, for example. This allows at least one component to be partially or substantially completely separated from the mixture. Specific separation methods may include contacting the mixture with the molecular sieve or molecular sieve composition to selectively adsorb the component. Examples of adsorbents include adsorbents that selectively adsorb water from cyclohexane.

[0094] According to this application, SCM-41 molecular sieves, silicon-germanium molecular sieves immediately after synthesis, or molecular sieve compositions may be used directly, or they may be used as catalysts (or as catalytically active components thereof) after undergoing necessary processing or transformations (such as ion exchange) conventionally performed in the art on the molecular sieves. In certain embodiments, for example, reactants (such as hydrocarbons) may be subjected to a predetermined reaction in the presence of a catalyst, thereby obtaining a target product. Examples of catalysts include catalysts for reacting benzene with ethylene to produce ethylbenzene.

[0095] [Examples] The technical solutions of this application will be further described in detail through the following embodiments, but the scope of protection of this application is not limited to these embodiments.

[0096] In the following examples and comparative examples, the specific surface area, pore volume, and micropore volume of the molecular sieves were determined by nitrogen physicoadsorption. The specific surface area was calculated using the BET method with a point range of relative pressure p / p0 = 0.01 to 0.1; the total pore volume was calculated using the adsorption amount corresponding to a relative pressure p / p0 = 0.99; and the micropore volume was calculated using the t-plot method. The nitrogen physicoadsorption-desorption experimental conditions were as follows: the test was performed using a MicrotracBEL Belsorp Max-II physicoadsorption apparatus at a measurement temperature of 77K; the molecular sieves were pre-treated with nitrogen as an adsorbent under vacuum at 350°C for 6 hours before measurement.

[0097] In the following examples and comparative examples, the X-ray diffraction (XRD) patterns of molecular sieve products were measured using a Panalytical X PERPRO X-ray powder diffractometer with a Cu Kα radiation source to analyze the material phase of the sample, with a Kα wavelength λ = 1.5405980 Å, nickel filter, 2θ scan range 2 to 50°, operating voltage 40 kV, current 40 mA, and scan speed 10° / min.

[0098] In the following examples and comparative examples, scanning electron microscope (SEM) images were obtained using a Hitachi S-4800II field emission scanning electron microscope (Japan) at a test voltage of 3kV and a test current of 10mA.

[0099] In the following examples and comparative examples, the natural tile structure of the molecular sieve framework topology was obtained using TOPOS software, and this structural model was plotted using 3dt software; the unit cell parameters of the molecular sieve were obtained using powder X-ray diffraction pattern indexing and simulation software; and the crystal structure of the molecular sieve was determined by analysis and refinement of 3D electron diffraction data, which was automatically collected by Instamatic software integrated into a JEOL JEM2100 transmission electron microscope. Structural analysis and refinement were performed using SHELXT and SHELXLE software, respectively.

[0100] In the following examples and comparative examples, the content of Si, Ge, and element X in the molecular sieve was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the content of F, organic template Q, and water was measured by thermogravimetric analysis.

[0101] In the following examples and comparative examples, unless otherwise specified, the reagents and raw materials used were commercially available products with analytical grade purity.

[0102] In the following examples and comparative examples, operating procedures and methods where no specific conditions are indicated were performed according to conventional methods and conditions, or according to the commercial instruction manual for the relevant equipment.

[0103] Example 1 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 1.57 g of water, 1.2 g of germanium oxide was added, and 4.29 g of Ludox silica sol (SiO2 40 wt%) was slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 1.5 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and placed in an oven at 155°C for 168 hours to crystallize. After the reaction, the solid was filtered, washed with distilled water, and dried at 100°C to obtain a powder solid immediately after the formation of the molecular sieve immediately after synthesis (schematic chemical composition: 0.09F·0.09Q·SiO2·0.4GeO2·0.14H2O). The powder solid immediately after production was placed in a muffle furnace and calcined at 550°C for 5 hours to obtain the final product, SCM-41 molecular sieve.

[0104] One framework topology of the final product SCM-41 molecular sieve is [4 6 ], [4 4 .6 2 ], [4 2 .5 4 ], [4 2 .5 4 .6 2 ], [4 7 .5 6 .6 9 .10 4 The smallest repeating unit of the framework topology of the SCM-41 molecular sieve is two [4] (see Figure 1a), which include natural tiles. 6 ], two [4 4 .6 2 ], two [4 2 .5 4 ], one [4 2 .5 4 .6 2 ], two [4 7 .5 6 .6 9 .10 4 Composed of natural tiles of ], this tiling structure is shown in Figure 1b. Another framework topology of this SCM-41 molecular sieve is [4 6 ], [4 4 .6 2, [4 2 .5 4 , [4 2 .6 4 , [4 14 .5 8 .6 16 .10 8 including natural tiles (see Figure 2a); the smallest repeating unit of the framework topology of the SCM-41 molecular sieve consists of two [4 6 , two [4 4 .6 2 , two [4 2 .5 4 , one [4 2 .6 4 , two [4 14 .5 6 .6 16 .10 8 of natural tiles, and this tiling structure is shown in Figure 2b.

[0105] This SCM-41 molecular sieve has intersecting linear channels with 10-member ring openings along the

[0010] and

[0110] directions of the crystal (see Figures 3 and 4). The planar projection of the channels with 10-member ring openings of this SCM-41 molecular sieve is an ellipse. The elliptical pores have a major axis of 6.0 - 7.0 Å and a minor axis of 4.4 - 5.4 Å.

[0106] The XRD pattern of this SCM-41 molecular sieve is shown in Figure 5A, and the pattern data are listed in Table 1A; the XRD pattern of the as-synthesized molecular sieve obtained in Example 1 is shown in Figure 5B, and the pattern data are listed in Table 1B. The three-dimensional electron diffraction data parameters, analysis results, and refinement results for the powder sample immediately after the formation of the as-synthesized molecular sieve are shown in Tables 2 - 4.

[0107] The SEM image of this SCM-41 molecular sieve is shown in Figure 6. It can be observed from Figure 6 that the SCM-41 molecular sieve is in a plate-like form. The nitrogen adsorption-desorption isotherm is shown in Figure 7. It can be seen from Figure 7 that the SCM-41 molecular sieve has a Type I isotherm, a specific surface area of 507 m 2 / g, and a pore volume of 0.19 cm 3It is observed that it has a micropore volume of / g. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8. [Table 15] [Table 16] [Table 17] TIFF2026511330000020.tif88169 [Table 18] TIFF2026511330000022.tif64169 [Table 19]

[0108] Example 2 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 0.24 g of water, 0.7 g of germanium oxide was added, and 0.7 g of Ludox silica sol (SiO2 40 wt%) was slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 3 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 155°C for 192 hours. After the reaction, the solid was filtered, washed, and dried to obtain the molecular sieve immediately after synthesis. This molecular sieve was then calcined to obtain the final molecular sieve product.

[0109] The XRD pattern of the obtained molecular sieve product is shown in Figure 8A; from Figure 8A, it can be seen that the product is an SCM-41 molecular sieve, and the pattern data is shown in Table 5A; the XRD pattern of the molecular sieve obtained immediately after synthesis is shown in Figure 8B, and the pattern data is shown in Table 5B.

[0110] Figure 9 shows an SEM image of the obtained SCM-41 molecular sieve; from Figure 9, it can be seen that this SCM-41 molecular sieve has a plate-like morphology. The nitrogen adsorption-desorption isotherm is shown in Figure 10. From Figure 10, it can be seen that this SCM-41 molecular sieve has a type I isotherm, 414m 2 Specific surface area per g, and 0.15 cm² 3 It can be observed that it has a micropore volume of / g. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8. [Table 20] [Table 21]

[0111] Example 3 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 2.65 g of water, 1.4 g of germanium oxide was added, and 4 g of Ludox silica sol (SiO2 40 wt%) was slowly added under stirring. Stirring was continued at room temperature for 4 hours. Finally, 4 g of ammonium fluoride solution (37 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 150°C for 144 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a specific surface area of ​​445 m². 2 The value is / g, and the micropore volume is 0.16 cm³. 3 The final SCM-41 molecular sieve product was obtained, with a concentration of / g and an XRD pattern similar to that shown in Figure 5. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8.

[0112] Example 4 7.36 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 4.3 g of water, 0.84 g of germanium oxide was added, and 2.02 g of fumed silica (SiO2 95 wt%) was slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 3 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 160°C for 120 hours. After the reaction, the solid was filtered, washed, and dried to obtain a molecular sieve immediately after synthesis. This molecular sieve was then calcined to obtain a specific surface area of ​​477 m². 2 The value is / g, and the micropore volume is 0.17 cm³. 3 The final SCM-41 molecular sieve product was obtained with a concentration of / g and possessing the XRD pattern data shown in Table 6A. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8. The diffraction peak positions of the XRD pattern of the molecular sieve immediately after synthesis were basically the same as those of the obtained SCM-41 molecular sieve, except that no clear diffraction peaks were observed at 13.05° and 14.19° of 2θ. The pattern data are listed in Table 6B. [Table 22] [Table 23]

[0113] Example 5 9.82 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 0.7 g of water, 0.38 g of germanium oxide was added, and 3 g of Ludox silica sol (SiO2 40 wt%) and 1.04 g of fumed silica (SiO2 95 wt%) were slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 0.051 g of SCM-41 molecular sieve obtained in Example 1 was added as a seed crystal, 3 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 165°C for 216 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a specific surface area of ​​423 m². 2 The value is / g, and the micropore volume is 0.16 cm³. 3 The final SCM-41 molecular sieve product was obtained, with a concentration of / g and an XRD pattern similar to that shown in Figure 5. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8.

[0114] Example 6 7.85 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 0.6 g of water, 1.05 g of germanium oxide was added, and 4.5 g of Ludox silica sol (SiO2 40 wt%) was slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 2.4 g of hydrofluoric acid (40 wt%) and 1.6 g of ammonium fluoride solution (37 wt%) were added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 145°C for 192 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a specific surface area of ​​488 m². 2 The value is / g, and the micropore volume is 0.18 cm³. 3 The final SCM-41 molecular sieve product was obtained, with a concentration of / g and an XRD pattern similar to that shown in Figure 5. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8.

[0115] Example 7 5.89 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 0.6 g of water, and 0.49 g of germanium oxide was added. Under stirring, 3 g of Ludox silica sol (SiO2 40 wt%) and 0.96 g of fumed silica (SiO2 95 wt%) were slowly added, and stirring was continued at room temperature for 4 hours. Finally, 2.4 g of hydrofluoric acid (40 wt%) and 2.4 g of ammonium fluoride solution (37 wt%) were added, and stirring was continued for 1 hour. After that, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 160°C for 192 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a specific surface area of ​​435 m². 2 The value is / g, and the micropore volume is 0.16 cm³. 3 The final SCM-41 molecular sieve product was obtained, with a concentration of / g and an XRD pattern similar to that shown in Figure 5. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8.

[0116] Example 8 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 3.1 g of water, 1.2 g of germanium oxide and 0.204 g of titanium sulfate were added, and 4.29 g of Ludox silica sol (SiO2 40 wt%) was slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 2 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 160°C for 168 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a specific surface area of ​​490 m². 2 The value is / g, and the micropore volume is 0.18 cm³. 3 The final SCM-41 molecular sieve product was obtained, with a concentration of / g and an XRD pattern similar to that shown in Figure 5. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8.

[0117] Example 9 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 0.55 g of water, and 0.7 g of germanium oxide was added. Under stirring, 0.34 g of Al2(SO4)3 solution (20% by weight) and 5 g of Ludox silica sol (SiO2 40% by weight) were added sequentially and slowly, and stirring was continued at room temperature for 4 hours. Finally, 3 g of hydrofluoric acid (40% by weight) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 155°C for 192 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a specific surface area of ​​482 m². 2 The value is / g, and the micropore volume is 0.18 cm³. 3 The final SCM-41 molecular sieve product was obtained, with a concentration of / g and an XRD pattern similar to that shown in Figure 5. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8.

[0118] Example 10 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was homogeneously mixed with 4.3 g of water, 1.2 g of germanium oxide was added, and 3.42 g of Al2(SO4)3 solution (20% by weight) and 4.29 g of Ludox silica sol (SiO2 40% by weight) were added sequentially under stirring, and stirring was continued at room temperature for 4 hours. Finally, 2 g of hydrofluoric acid (40% by weight) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 155°C for 168 hours. After the reaction, the solid was filtered, washed, and dried to obtain a molecular sieve immediately after synthesis (schematic chemical composition: 0.11F·0.11Q·SiO2·0.38GeO2·0.023Al2O3·0.20H2O). This molecular sieve, immediately after synthesis, is then calcined, resulting in a specific surface area of ​​462 m². 2 The value is / g, and the micropore volume is 0.17 cm³. 3The final SCM-41 molecular sieve product was obtained with a ratio of / g and possessing the XRD pattern data shown in Table 7A. The raw material ratios for the synthesis of this molecular sieve are shown in Table 8. The diffraction peak positions of the XRD pattern of the molecular sieve immediately after synthesis were essentially the same as those of the obtained SCM-41 molecular sieve, except that no clear diffraction peaks were observed at 13.05° and 14.19° of 2θ. The pattern data are listed in Table 7B. [Table 24] [Table 25] [Table 26]

[0119] Comparative Example 1 5.45 g of tris(dimethylaminopropyl)amine was homogeneously mixed with 1.57 g of water, 1.2 g of germanium oxide was added, and 4.29 g of Ludox silica sol (SiO2 40 wt%) was slowly added under stirring, and stirring was continued at room temperature for 4 hours. Finally, 1.5 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. Then, the above mixture was packed into a crystallization vessel equipped with a polytetrafluoroethylene liner and crystallized in an oven at 155°C for 168 hours. After the reaction, the solid was filtered, washed with distilled water, and dried at 100°C to obtain a powder solid immediately after synthesis of the molecular sieve. This powder solid immediately after synthesis was placed in a muffle furnace and calcined at 550°C for 5 hours to obtain a BEC molecular sieve. The XRD pattern of the obtained BEC molecular sieve is shown in Figure 11.

[0120] Application Example 1 Two grams of the SCM-41 molecular sieve synthesized in Example 1 were thoroughly mixed with 1.6 grams of boehmite and 0.2 grams of sesbania gum powder. 5 ml of 5% by weight nitric acid was added and kneaded, and the mixture was extruded into a strip with a diameter of φ1.6 × 2 mm. The strip was then dried at 120°C and calcined at 550°C for 3 hours in an air atmosphere to produce the SCM-41 molecular sieve composition.

[0121] Test Example 1 Two grams of the SCM-41 molecular sieve synthesized in Example 1 or the SCM-41 molecular sieve composition prepared in Example 12 were poured into a 100 ml weighing bottle, immediately sealed with the bottle cap, and weighed. The bottle cap was then opened, and the bottle was placed in a desiccator containing approximately 1000 ml of saturated sodium chloride aqueous solution. Adsorption was carried out at a constant temperature of 30-35°C for 24 hours. The desiccator lid was opened. The weighing bottle was immediately covered with its cap and weighed (to an accuracy of 0.2 mg). The static adsorption capacity of the molecular sieve to water was calculated according to the following formula. The results are shown in Table 9: Adsorption capacity = (Weight of sample after adsorption - Weight of initial sample) / Weight of initial sample × 100%.

[0122] Molecular sieves of 4A, ZSM-5, Beta, and NaY were tested using the method described above. The resulting static adsorption capacities for water are also shown in Table 9.

[0123] Test Example 2 Two grams of the SCM-41 molecular sieve synthesized in Example 1 or the SCM-41 molecular sieve composition prepared in Example 12 were poured into a 100 ml weighing bottle, immediately sealed with the bottle cap, and weighed. The bottle cap was then opened, and the bottle was placed in a desiccator connected to a vacuum pump. The pressure inside the desiccator was reduced to less than 1000 Pa by suction. The vacuum pump valve was closed, the valve for the organic adsorbent was opened, and the organic adsorbent was connected to the desiccator. Adsorption was carried out at 30-35°C for 24 hours under the saturated vapor pressure of the organic adsorbent. The valve for the organic adsorbent was closed, the desiccator was evacuated, and then the desiccator cap was opened. The weighing bottle was immediately covered with the bottle cap and weighed (to an accuracy of 0.2 mg). The static adsorption capacity of the molecular sieve for organic matter was calculated according to the following formula. The results are shown in Table 9: Adsorption capacity = (Weight of sample after adsorption - Weight of initial sample) / Weight of initial sample × 100%.

[0124] Molecular sieves of 4A, ZSM-5, Beta, and NaY were tested using the method described above. The static adsorption capacities for the resulting organic substances are also shown in Table 9. [Table 27]

[0125] From Table 9 above, it can be seen that the SCM-41 molecular sieve and its composition according to the present invention can be used as an adsorbent for many organic low molecular weights and water, and exhibits particularly excellent adsorption performance for H2O.

[0126] Preferred embodiments of this application are detailed above. However, this application is not limited thereto. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solutions of this application, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be deemed to be disclosed in this application and are included within the scope of protection of this application. [Brief explanation of the drawing]

[0127] [Figure 1] Figure 1 shows a schematic diagram (a) of the natural tile set in the framework of the SCM-41 molecular sieve obtained in Example 1, and its tiling structure (b). [Figure 2] Figure 2 shows a schematic diagram (a) and its tiling structure (b) of another set of natural tiles in the framework of the SCM-41 molecular sieve obtained in Example 1. [Figure 3] Figure 3 shows projections from different directions of one framework structure of the SCM-41 molecular sieve obtained in Example 1. [Figure 4] Figure 4 shows projections from different directions of another framework structure of the SCM-41 molecular sieve obtained in Example 1. [Figure 5A] Figures 5A and 5B show the X-ray diffraction (XRD) patterns of the SCM-41 molecular sieve obtained in Example 1 and the molecular sieve immediately after synthesis. [Figure 5B] Figures 5A and 5B show the X-ray diffraction (XRD) patterns of the SCM-41 molecular sieve obtained in Example 1 and the molecular sieve immediately after synthesis. [Figure 6] Figure 6 shows a scanning electron microscope (SEM) image of the SCM-41 molecular sieve obtained in Example 1. [Figure 7] Figure 7 shows the nitrogen adsorption-desorption isotherm of the SCM-41 molecular sieve obtained in Example 1. [Figure 8A] Figures 8A and 8B show the XRD patterns of the SCM-41 molecular sieve obtained in Example 2 and the molecular sieve immediately after synthesis, respectively. [Figure 8B] Figures 8A and 8B show the XRD patterns of the SCM-41 molecular sieve obtained in Example 2 and the molecular sieve immediately after synthesis, respectively. [Figure 9] Figure 9 shows an SEM image of the SCM-41 molecular sieve obtained in Example 2. [Figure 10] Figure 10 shows the nitrogen adsorption-desorption isotherm of the SCM-41 molecular sieve obtained in Example 2. [Figure 11] Figure 11 shows the XRD pattern of the BEC molecular sieve obtained in Comparative Example 1.

Claims

1. A silicon-germanium molecular sieve exhibiting an X-ray diffraction pattern showing the X-ray diffraction peaks shown in the table below: Table 1 。

2. The silicon-germanium molecular sieve according to claim 1, exhibiting the X-ray diffraction peaks shown in the table below: Table 2 。

3. The silicon-germanium molecular sieve according to claim 1 or 2, wherein the X-ray diffraction pattern of the molecular sieve further exhibits one or more X-ray diffraction peaks as shown in the following table: Table 3 。

4. The silicon-germanium molecular sieve according to any one of claims 1 to 3, wherein the X-ray diffraction pattern of the molecular sieve further shows one or more X-ray diffraction peaks as shown in the table below: Table 4 。

5. The silicon-germanium molecular sieve according to any one of claims 1 to 4, wherein the X-ray diffraction pattern of the molecular sieve exhibits the relative intensity characteristics of the diffraction peaks shown in the following table: Table 5 。

6. The silicon-germanium molecular sieve according to claim 5, wherein the X-ray diffraction pattern further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: Table 6 。

7. The silicon-germanium molecular sieve according to claim 5 or 6, wherein the X-ray diffraction pattern further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: Table 7 。

8. The silicon-germanium molecular sieve according to any one of claims 1 to 7, wherein the molecular sieve satisfies at least one of the following conditions (a) to (h): (a) The molecular sieve has a framework topology including natural tiles of [[4 ６ , [[4 ４ . 6 ２ , [[4 ２ . 5 ４ , [[4 ２ . 5 ４ . 6 ２ , [[4 ７ . 5 ６ . 6 ９ . 10 ４ ; (b) The molecular sieve has two [4 ６ ], two [4 ４ 6. ２ ], two [4 ２ 5. ４ ], one [4 ２ 5. ４ 6. ２ ], two [4 ７ 5. ６ 6. ９ 10 ４ The framework topology has the smallest repeating unit composed of natural tiles; (c) the molecular sieve is [4 ６ ], [4 ４ 6. ２ ], [4 ２ 5. ４ ], [4 ２ 6. ４ ], [4 １４ 5. ８ 6. １６ 10 ８ It has a framework topology that includes natural tiles of ]; (d) The molecular sieve has two [4 ６ ], two [4 ４ 6. ２ ], two [4 ２ 5. ４ ], one [4 ２ 6. ４ ], two [4 １４ 5. ８ 6. １６ 10 ８ The framework topology has the smallest repeating unit composed of natural tiles; (e) The molecular sieve has intersecting linear channels having 10-membered ring openings along the [010] and [110] directions of the crystal; Preferably, the linear channel having a 10-membered ring opening has an elliptical planar projection; More preferably, the ellipse has a major axis of 6.0 to 7.0 Å, preferably 6.1 to 6.9 Å, and more preferably 6.2 to 6.8 Å; More preferably, the ellipse has a minor axis of 4.4 to 5.4 Å, preferably 4.5 to 5.3 Å, and more preferably 4.6 to 5.2 Å; (f) The molecular sieve belongs to the monoclinic system; Preferably, the molecular sieve has a unit cell parameter including a = 17.0 to 19.0 Å, preferably a = 17.2 to 18.8 Å, and more preferably a = 17.4 to 18.6 Å; Preferably, the molecular sieve has unit cell parameters including b = 12.6 to 14.6 Å, preferably b = 12.8 to 14.4 Å, and more preferably b = 13.0 to 14.2 Å; Preferably, the molecular sieve has unit cell parameters including c = 21.2 to 23.2 Å, preferably c = 21.4 to 23.0 Å, and more preferably c = 21.6 to 22.8 Å; Preferably, the molecular sieve has unit cell parameters including α = 90° and γ = 90°; Preferably, the molecular sieve has a unit cell parameter of β = 96 to 106°, preferably β = 97 to 105°, and more preferably β = 98 to 104°; (g) The molecular sieve is 250 to 1000 m ２ / g, preferably 300 to 800m ２ It has a specific surface area of ​​ / g; (h) The molecular sieve is 0.1 to 0.4 cm. ３ / g, preferably 0.12 to 0.35 cm ３ It has a micropore volume of / g.

9. The molecular sieve contains SiO in a ratio of (0.25-25):1, preferably (0.5-20):1, more preferably (1-15):1, and even more preferably (1.5-10):

1. ２ / GeO ２ A silicon-germanium molecular sieve according to any one of claims 1 to 8, having a molar ratio.

10. The molecular sieve further comprises additional elements X selected from boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, indium, or combinations thereof, preferably additional elements X selected from aluminum and titanium, preferably at least a portion of the additional elements X present in oxide form; Preferably, when calculated on a molar basis of elements, the ratio of the total molar content of silicon and germanium to the total molar content of all additional elements X in the molecular sieve is 5 or more, preferably 10 or more, more preferably 10 to 100, the silicon-germanium molecular sieve according to any one of claims 1 to 9.

11. Formula “kF・mQ・SiO ２ ・1 / nGeO ２ pH ２ O" or "kF・mQ・SiO ２ ・1 / nGeO ２ qXO ｙ／２ pH ２ A silicon-germanium molecular sieve according to claim 1, having a schematic chemical composition represented by "O", wherein Q is an organic template, X is an element selected from boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, indium, or a combination thereof, preferably an element selected from aluminum and titanium, and y is the valence of element X, in the range of 1 to 7. Here, 0.25 ≤ n ≤ 25, preferably 0.5 ≤ n ≤ 20, more preferably 1 ≤ n ≤ 15, and particularly preferably 1.5 ≤ n ≤ 10; 0.05 ≤ k ≤ 1.0, preferably 0.05 ≤ k ≤ 0.5, more preferably 0.1 ≤ k ≤ 0.5, and particularly preferably 0.1 ≤ k ≤ 0.4; 0.01 ≤ m ≤ 1.0, preferably 0.02 ≤ m ≤ 0.5, more preferably 0.05 ≤ m ≤ 0.5, and particularly preferably 0.05 ≤ m ≤ 0.3; 0.005 ≤ p ≤ 0.5, preferably 0.01 ≤ p ≤ 0.4, more preferably 0.01 ≤ p ≤ 0.3, and particularly preferably 0.02 ≤ p ≤ 0.2; 0 ≤ q ≤ (1 + 1 / n) / 5, preferably 0 ≤ q ≤ (1 + 1 / n) / 10, more preferably (1 + 1 / n) / 100 ≤ q ≤ (1 + 1 / n) / 10; The organic template Q contains 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, or consists of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol; Preferably, the X-ray diffraction pattern of the silicon-germanium molecular sieve further exhibits one or more X-ray diffraction peaks as shown in the following table: Table 8 More preferably, the silicon-germanium molecular sieve exhibits an X-ray diffraction pattern that shows one or more X-ray diffraction peaks as shown in the table below: Table 9 。

12. The X-ray diffraction pattern of the molecular sieve exhibits the relative intensity characteristics of the diffraction peaks shown in the following table: Table 10 Preferably, the X-ray diffraction pattern of the molecular sieve further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: Table 11 More preferably, the silicon-germanium molecular sieve according to claim 11, wherein the X-ray diffraction pattern of the molecular sieve further exhibits the relative intensity characteristics of the diffraction peaks shown in one or more rows of the following table: Table 12 。

13. A method for producing a silicon-germanium molecular sieve according to any one of claims 1 to 12, comprising the steps of: mixing a silicon source, a germanium source, a fluorine source, an organic template Q, water, and an optional additional element X source to obtain the silicon-germanium molecular sieve; subjecting to a crystallization reaction; and optionally calcining, wherein the organic template Q contains 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol or consists of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol].

14. The manufacturing method according to claim 13, having one or more of the following features: The silicon source is selected from water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomite, zeolite molecular sieve, tetraethyl orthosilicate, or a combination thereof; The germanium source is selected from germanium oxide, germanium nitrate, tetraalkoxygermanium, or a combination thereof; The fluorine source is selected from hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride, or a combination thereof, preferably selected from hydrofluoric acid and ammonium fluoride; and The additional element X source is selected from a boron source, an aluminum source, a gallium source, a titanium source, a zirconium source, a hafnium source, a tin source, a zinc source, an iron source, a chromium source, an indium source, or a combination thereof; preferably, it is selected from a boron oxide source, an aluminum oxide source, a gallium oxide source, a titanium oxide source, a zirconium oxide source, a hafnium oxide source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, an indium oxide source, or a combination thereof.

15. A method for manufacturing according to claim 13 or 14, having one or more of the following features: The organic template Q, the silicon source (SiO ２ Calculated as ） , the germanium source (GeO ２ (Calculated as F) The molar ratio of the amount of fluorine source (calculated as F) and water is (0.15-4):(0.2-0.97):(0.03-0.8):(0.2-4):(0.5-30), preferably (0.15-4):(0.2-0.9615):(0.0385-0.8):(0.2-4):(0.5-30), more preferably (0.25-3.5):( 0.3-0.96): (0.04-0.7): (0.35-3.5): (1-25), more preferably (0.3-2.5): (0.5-0.94): (0.06-0.5): (0.4-2.5): (2-20), even more preferably (0.35-1.5): (0.6-0.91): (0.09-0.4): (0.45-2): (3-15); The total molar amount of the additional element X source (calculated as element X) and the silicon source (SiO ２ (calculated as) and the germanium source (GeO ２ The ratio of the total molar amount (calculated as) to the total molar amount is (0 to 0.2):1, preferably (0 to 0.1):1, and more preferably (0.01 to 0.01):1; The crystallization reaction is carried out under the following conditions: a crystallization temperature of 100 to 200°C, preferably 110 to 190°C, more preferably 120 to 180°C; a crystallization time of 24 to 360 hours, preferably 48 to 300 hours, more preferably 72 to 240 hours; The firing is carried out under the following conditions: a firing temperature of 300 to 750°C, preferably 400 to 600°C; and a firing time of 1 to 10 hours, preferably 3 to 6 hours.

16. A molecular sieve composition comprising a silicon-germanium molecular sieve according to any one of claims 1 to 12, and an active ingredient and / or binder, wherein the active ingredient is selected from natural or synthetic zeolites, and the binder is selected from clay, white clay, silica gel, alumina, or a combination thereof.

17. Use of the silicon-germanium molecular sieve according to any one of claims 1 to 12 or the molecular sieve composition according to claim 16 as an adsorbent or catalyst.

Images