SCM-41 Molecular Sieves, Their Preparation Methods, and Applications

Abstract

This invention relates to a novel SCM-41 molecular sieve, its preparation method, and its applications. The SCM-41 molecular sieve has a unique X-ray diffraction pattern and shows promising application prospects in adsorption separation, ion exchange, and catalytic conversion of organic compounds.

Description

Technical Field

[0001] This invention belongs to the field of molecular sieve technology, specifically relating to an SCM-41 molecular sieve, its preparation method and application, as well as an SCM-41 molecular sieve composition and its application. Background Technology

[0002] Molecular sieves are an important class of microporous crystalline materials, possessing regular and ordered molecular-scale pore structures, tunable chemical compositions, strong acidity, and high hydrothermal stability. They are currently widely used in catalysis, adsorption, and ion exchange. The superior performance of molecular sieves is highly dependent on their framework structure; therefore, synthesizing molecular sieves with special framework structures has always been one of the most important research directions in the field. Currently, more than 250 molecular sieves with novel framework structures have been discovered. The framework structure of molecular sieves is usually composed of coordination tetrahedra (TO4) connected by shared vertices (generally oxygen atoms). In zeolite molecular sieves, the tetrahedra in the framework structure are SiO4 tetrahedra and AlO4 tetrahedra. These two types of tetrahedra in zeolite molecular sieves can be replaced by other types of tetrahedra to form molecular sieves or zeolite-like structures with different framework structures. For example, AlO4 tetrahedra can be replaced by GaO4 or ZnO4 tetrahedra, thus forming the framework of heteroatom molecular sieves together with SiO4 tetrahedra; Ge and Si have similar coordination properties and can also form tetrahedral coordination structures. Numerous germanium-containing molecular sieves or sieve-like structures can be formed through the linkage of GeO4 and SiO4. However, to date, no material with the same X-ray diffraction crystal structure as SCM-41 molecular sieve has been discovered. Summary of the Invention

[0003] This invention provides an SCM-41 molecular sieve, its preparation method, and its application.

[0004] A first aspect of the present invention provides an SCM-41 molecular sieve, wherein the X-ray diffraction pattern of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the table below:

[0005]

[0006] In some embodiments, the X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below:

[0007]

[0008] In some embodiments, the X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below:

[0009]

[0010] In some embodiments, the X-ray diffraction pattern of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the table below:

[0011]

[0012] In some embodiments, the X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below:

[0013]

[0014] In some embodiments, the X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below.

[0015]

[0016] In some embodiments, the framework topology of the SCM-41 molecular sieve includes [4] 6 ]、[4 4 0.6 2 ]、[4 2 0.5 4 ]、[4 2 0.5 4 0.6 2 ]、[4 7 0.5 6 0.6 9 .10 4 Natural splicing structure, such as Figure 1 As shown in a.

[0017] In some embodiments, the framework topological minimal repeating unit of the SCM-41 molecular sieve consists of 2 [4] 6 ], 2 [4 4 0.6 2 ], 2 [4 2 0.5 4 ], 1 [4 2 0.5 4 0.6 2 ], 2 [4 7 0.5 6 0.6 9 .10 4 Composed of naturally joined structures, such as Figure 1 As shown in b.

[0018] In some embodiments, the framework topology of the SCM-41 molecular sieve includes [4] 6 ]、[4 4 0.6 2 ]、[4 2 0.5 4 ]、[4 2 0.6 4]、[4 14 0.5 8 0.6 16 .10 8 Natural splicing structure, such as Figure 2 As shown in a.

[0019] In some embodiments, the framework topological minimal repeating unit of the SCM-41 molecular sieve consists of 2 [4] 6 ], 2 [4 4 0.6 2 ], 2 [4 2 0.5 4 ], 1 [4 2 0.6 4 ], 2 [4 14 0.5 8 0.6 16 .10 8 Composed of naturally joined structures, such as Figure 2 As shown in b.

[0020] In some embodiments, the SCM-41 molecular sieve has intersecting 10-membered ring-shaped cylindrical channels along the

[010] and

[110] directions of the crystal.

[0021] In some embodiments, the planar projection of the 10-membered ring open cylindrical channel of the SCM-41 molecular sieve is elliptical.

[0022] In some embodiments, the major axis of the ellipse is Preferred More

[0023] In some embodiments, the minor axis of the ellipse is Preferred More

[0024] In some embodiments, the SCM-41 molecular sieve belongs to the monoclinic crystal system.

[0025] In some embodiments, the cell parameters of the SCM-41 molecular sieve are: Preferred More

[0026] In some embodiments, the cell parameters of the SCM-41 molecular sieve are: Preferred More

[0027] In some embodiments, the cell parameters of the SCM-41 molecular sieve are: Preferred More

[0028] In some embodiments, the cell parameters of the SCM-41 molecular sieve are α = 90° and γ = 90°.

[0029] In some embodiments, the cell parameters of the SCM-41 molecular sieve are β = 96–106°, preferably β = 97–105°, and more preferably β = 98–104°.

[0030] In some embodiments, the SCM-41 molecular sieve comprises SiO2 and GeO2. Preferably, the molar ratio of SiO2 to GeO2 is (0.25-25):1, more preferably (0.5-20):1, more preferably (1-15):1, and even more preferably (1.5-10):1. In some specific embodiments, the molar ratio of SiO2 to GeO2 is 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 between them.

[0031] In some embodiments, the calcined SCM-41 molecular sieve has an illustrative chemical composition as shown in the formula "SiO2·1 / nGeO2", wherein the silicon-germanium molar ratio is 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and even more preferably 1.5≤n≤10. In some specific embodiments, the value of n can be 0.25, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, or any value between them.

[0032] In some embodiments, the SCM-41 molecular sieve in its synthetic state has an illustrative chemical composition as shown in the formula "kF·mQ·SiO2·1 / nGeO2·pH2O", where Q is an organic template agent.

[0033] 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and even more preferably 1.5≤n≤10;

[0034] 0.05≤k≤1.0, preferably 0.05≤k≤0.5, more preferably 0.1≤k≤0.5, and even more preferably 0.1≤k≤0.4;

[0035] 0.01≤m≤1.0, preferably 0.02≤m≤0.5, more preferably 0.05≤m≤0.5, and even more preferably 0.05≤m≤0.3;

[0036] 0.005≤p≤0.5, preferably 0.01≤p≤0.4, more preferably 0.01≤p≤0.3, and even more preferably 0.02≤p≤0.2.

[0037] In some embodiments, the organic template agent is selected from substances containing 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol. In some embodiments, the organic template agent is a substance containing 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, or 1-[bis(3-dimethylaminopropyl)amino]-2-propanol, or 1-[Bis[3-(dimethylamino)propyl]amino]-2-propanol, with the following structural formula:

[0038] The present invention uses an organic template agent with the above-mentioned specific structure to prepare SCM-41 molecular sieve.

[0039] In some embodiments, the silicon and germanium elements in the SCM-41 molecular sieve may be replaced by X atoms, and the SCM-41 molecular sieve may also contain an oxide of the X element. Preferably, the X element is selected from at least one of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, and indium, and more preferably from aluminum and / or titanium.

[0040] In some embodiments, the ratio of the sum of the molar contents of Si and Ge elements to the molar contents of X element, based on the molar content of the elements, is ≥5, preferably ≥10, and more preferably 10-100. In some specific embodiments, the ratio of the sum of the molar contents of Si and Ge elements to the molar content of X element, based on the molar content of the elements, can be 5, 10, 20, 40, 60, 80, 100, 150, 200, or any value between them.

[0041] In some embodiments, the specific surface area (BET method) of the SCM-41 molecular sieve is 250-1000 m². 2 / g, preferably 300-800m 2 / g.

[0042] In some embodiments, the micropore volume (t-plot method) of the SCM-41 molecular sieve is 0.1-0.4 cm³. 3 / g, preferably 0.12-0.35cm 3 / g.

[0043] A second aspect of the present invention provides a method for preparing SCM-41 molecular sieve, comprising the steps of mixing a silicon source, a germanium source, a fluorine source, an organic template agent Q, water, and optionally an X element source, and carrying out a crystallization reaction to obtain the SCM-41 molecular sieve, wherein the organic template agent Q comprises 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol.

[0044] In some embodiments, the structural formula of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol is shown below:

[0045]

[0046] In some embodiments, the preparation method further includes a calcination step.

[0047] In some embodiments, the silicon source is selected from at least one of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite molecular sieve, and tetraethyl orthosilicate.

[0048] In some embodiments, the germanium source is selected from at least one of germanium oxide, germanium nitrate, and tetraalkoxy germanium.

[0049] In some embodiments, the fluorine source includes at least one selected from hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, preferably selected from hydrofluoric acid and / or ammonium fluoride.

[0050] In some embodiments, the X element source is selected from at least one of boron source, aluminum source, gallium source, titanium source, zirconium source, hafnium source, tin source, zinc source, iron source, chromium source and indium source; preferably selected from at least one of boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, zirconium oxide source, hafnium oxide source, tin oxide source, zinc oxide source, iron oxide source, chromium oxide source and indium oxide source.

[0051] In some embodiments, the molar ratio of the organic template agent Q, the silicon source (calculated as SiO2), the germanium source (calculated as GeO2), the fluorine source (calculated as F), and water is (0.15-4):(0.2-1):(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 (0.2... 5-3.5):(0.3-0.96):(0.04-0.7):(0.35-3.5):(1-25), further preferably (0.3-2.5):(0.5-0.94):(0.06-0.5):(0.4-2.5):(2-20), further preferably (0.35-1.5):(0.6-0.91):(0.09-0.4):(0.45-2):(3-15).

[0052] In some embodiments, the X element source (in the form of oxide XO) m The ratio of the molar content of silicon source (calculated as SiO2 and GeO2) to the sum of the molar contents of silicon source and germanium source (calculated as SiO2 and GeO2) is (0-0.2):1, preferably (0-0.1):1, and more preferably (0.01-0.01):1.

[0053] In some embodiments, the crystallization reaction conditions include: crystallization 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.

[0054] In some embodiments, the calcination conditions include calcination at 300-750°C for 1-10 hours, preferably at 400-600°C for 3-6 hours.

[0055] A third aspect of the present invention provides a molecular sieve composition comprising the SCM-41 molecular sieve described in the first aspect or the SCM-41 molecular sieve prepared by the preparation method described in the second aspect, as well as active materials and / or inactive materials.

[0056] In some embodiments, the active material includes, but is not limited to, synthetic zeolites and natural zeolites.

[0057] In some embodiments, the inactive material (generally referred to as a binder) includes, but is not limited to, clay, kaolin, silica gel, and alumina.

[0058] The fourth aspect of the present invention provides the use of the SCM-41 molecular sieve described in the first aspect or the SCM-41 molecular sieve prepared by the preparation method described in the second aspect, or the molecular sieve composition described in the third aspect, as an adsorbent or catalyst.

[0059] The present invention has the following beneficial effects:

[0060] (1) This invention provides a novel SCM-41 molecular sieve, whose framework structure has never been obtained before in the field;

[0061] (2) The SCM-41 molecular sieve of the present invention has a regular molecular-sized pore structure, strong acidity, ion exchange performance and high thermal stability.

[0062] (3) The SCM-41 molecular sieve preparation method of the present invention has simple synthesis steps, strong operability, wide synthesis range, and is easy to promote. Attached Figure Description

[0063] Figure 1This is a schematic diagram (a) of the natural splicing of the framework topology of the SCM-41 molecular sieve obtained in Example 1 and a schematic diagram (b) of its composition.

[0064] Figure 2 This is a schematic diagram (a) of the natural splicing of the framework topology of the SCM-41 molecular sieve obtained in Example 1 and a schematic diagram (b) of its composition.

[0065] Figure 3 These are projection images of the framework structure of the SCM-41 molecular sieve obtained in Example 1 from different directions.

[0066] Figure 4 These are projection images of the framework structure of the SCM-41 molecular sieve obtained in Example 1 from different directions.

[0067] Figure 5 The image shows the X-ray diffraction (XRD) pattern of the sample obtained in Example 1.

[0068] Figure 6 This is a scanning electron microscope (SEM) image of the sample obtained in Example 1.

[0069] Figure 7 The nitrogen adsorption-desorption isotherm of the sample obtained in Example 1.

[0070] Figure 8 The image shows the X-ray diffraction (XRD) pattern of the sample obtained in Example 2.

[0071] Figure 9 This is a scanning electron microscope (SEM) image of the sample obtained in Example 2.

[0072] Figure 10 The nitrogen adsorption-desorption isotherm of the sample obtained in Example 2. Detailed Implementation

[0073] To facilitate understanding of the present invention, embodiments are provided below. However, those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as specific limitations on the invention. The endpoints of the ranges and any values ​​disclosed herein are not limited to those precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them.

[0074] All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used herein have the meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the definitions herein shall prevail.

[0075] In this paper, specific surface area refers to the total area per unit mass of a sample, including internal and external surface areas. Non-porous samples only have external surface area, such as silicate cement and some clay mineral powders; porous and multi-porous samples have both external and internal surface areas, such as asbestos fibers, diatomaceous earth, and molecular sieves. In porous and multi-porous samples, the surface area of ​​pores with a diameter less than 2 nm is the internal surface area, and the surface area after deducting 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.

[0076] In this paper, pore volume refers to the volume of pores per unit mass of porous material. Total pore volume refers to the volume of all pores per unit mass of molecular sieve (generally only pores with a channel diameter of less than 50 nm are included). Micropore volume refers to the volume of all micropores per unit mass of molecular sieve (generally referring to pores with a channel diameter of less than 2 nm).

[0077] In this paper, the specific surface area, pore volume, and micropore volume of the molecular sieve were determined by nitrogen physical adsorption under test conditions of 77 K. The specific surface area was calculated using the BET (Brunauer-Emmett-Teller) method, with points ranging from a relative pressure p / p0 of 0.01 to 0.1. The total pore volume was calculated using the adsorption amount corresponding to a relative pressure p / p0 = 0.99. The micropore volume was calculated using the t-plot method. All of the above test methods are well known to those skilled in the art.

[0078] In this paper, the structure of the molecular sieve was determined by X-ray diffraction (XRD). The XRD pattern of the SCM-41 molecular sieve was determined by X-ray powder diffraction using a Cu-Kα source with a Kα1 wavelength λ = 1.5405980 angstroms. Nickel filter.

[0079] In this paper, in the XRD data of molecular sieves, vw, w, m, s, and vs represent the relative intensities of diffraction peaks, where vw is very weak, w is weak, m is moderate, s is strong, and vs is very strong, which is well known to those skilled in the art. Generally, vw is less than 5, w is less than 20; m is 20-40 (inclusive of 20, excluding 40); s is 40-70 (inclusive of 40, excluding 70); and vs is greater than 70 (inclusive of 70).

[0080] In this paper, the natural topological assembly structure of the molecular sieve framework was obtained using TOPOS software, and the structural model was drawn using 3dt software. The unit cell parameters of the molecular sieve were obtained using powder XRD pattern indexing and simulation software. The crystal structure of the molecular sieve was determined through three-dimensional electron diffraction data analysis and refinement. The three-dimensional electron diffraction data were automatically collected using the Instamatic software built into a JEOL JEM2100 transmission electron microscope. The structural analysis and refinement were performed using SHELXT and SHELXLE software, respectively.

[0081] In this document, the SCM-41 molecular sieve has an illustrative chemical composition I as shown in the formula "SiO2·1 / n GeO2". It is known that molecular sieves sometimes contain a certain amount of water (especially immediately after synthesis), but the present invention considers it unnecessary to limit the amount of water, as its presence or absence does not substantially affect the XRD pattern of the molecular sieve. Therefore, the illustrative chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, it is evident that illustrative chemical composition I represents the framework chemical composition of the SCM-41 molecular sieve.

[0082] In this document, in the illustrative chemical composition I, the silicon-germanium molar ratio is 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and even more preferably 1.5≤n≤10.

[0083] In this document, immediately after synthesis, the molecular sieve may generally contain further organic matter (especially organic template agents) and water, such as those filling its pores. Therefore, the SCM-41 molecular sieve may also have an illustrative chemical composition II as shown in the formula "kF·mQ·SiO2·1 / nGeO2·pH2O". Here, by calcining the molecular sieve having the illustrative chemical composition II (sometimes referred to as the molecular sieve precursor) to remove any organic template agents and water present in its pores, a molecular sieve having the illustrative chemical composition I can be obtained. Furthermore, the calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally from 300°C to 750°C, preferably from 400°C to 600°C, and the calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. Additionally, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere. Therefore, the illustrative chemical composition I is sometimes referred to as the calcined illustrative chemical composition, while the illustrative chemical composition II is sometimes referred to as the synthetic illustrative chemical composition.

[0084] In this document, in the illustrative chemical composition II, the silicon-germanium molar ratio is 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and even more preferably 1.5≤n≤10.

[0085] In this document, in the illustrative chemical composition II, F is fluorine, 0.05≤k≤1.0, preferably 0.05≤k≤0.5, more preferably 0.1≤k≤0.5, and even more preferably 0.1≤k≤0.4.

[0086] In this document, in the illustrative chemical composition II, Q is an organic template agent, 0.01≤m≤1.0, preferably 0.02≤m≤0.5, more preferably 0.05≤m≤0.5, and even more preferably 0.05≤m≤0.3.

[0087] In this document, in the illustrative chemical composition II, the organic template agent is 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, with the following structural formula:

[0088]

[0089] In this document, in the illustrative chemical composition II, 0.005 ≤ p ≤ 0.5, preferably 0.01 ≤ p ≤ 0.4, more preferably 0.01 ≤ p ≤ 0.3, and even more preferably 0.02 ≤ p ≤ 0.2.

[0090] In this paper, in the SCM-41 molecular sieve, framework silicon and germanium can be partially replaced by non-silicon and non-germanium element X, with a substitution rate not exceeding 20%. Here, the parameter "substitution rate" is dimensionless. The non-silicon and non-germanium element X is selected from at least one element in the group consisting of boron, aluminum, tin, zirconium, and titanium, preferably at least one element in the group consisting of aluminum and titanium. Substitution rate = X / (Si+Ge)×100%, using moles when calculating the substitution rate.

[0091] In this document, the SCM-41 molecular sieve can be synthesized by a method comprising the step of crystallizing a mixture (hereinafter collectively referred to as the mixture) containing a silicon source, a germanium source, a fluorine source, an organic template agent Q, water, and an optional X element source to obtain the molecular sieve.

[0092] In this paper, in the method for preparing the molecular sieve, the organic template agent Q comprises 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, the structural formula of which is shown below:

[0093]

[0094] In this document, the crystallization step in the method for preparing the molecular sieve can be carried out in any manner conventionally known in the art, such as mixing the silicon source, the germanium source, the fluorine source, the organic template agent Q, water, and optionally the X element source in a predetermined ratio, and hydrothermally crystallizing the resulting mixture under the crystallization conditions. Stirring may be used as needed.

[0095] In this document, in the method for preparing the molecular sieve, any silicon source conventionally used in the art for this purpose can be used as the silicon source. These include, but are not limited to, water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite molecular sieves, or tetraethyl orthosilicate. These silicon sources can be used individually or in combination in the desired proportions.

[0096] In this document, in the method for preparing the molecular sieve, any germanium source conventionally used in the art for this purpose can be used as the germanium source, including but not limited to germanium oxide, germanium nitrate, and tetraalkoxy germanium.

[0097] In this document, in the method for preparing the molecular sieve, any fluorine source conventionally used in the art for this purpose can be used as the fluorine source, including but not limited to fluorides or aqueous solutions thereof, such as hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride, especially hydrofluoric acid, ammonium fluoride, etc.

[0098] In some embodiments, in the method for preparing the molecular sieve, the molar ratio of the organic template agent Q, the silicon source (calculated as SiO2), the germanium source (calculated as GeO2), the fluorine source (calculated as F), and water is (0.15-4):(0.2-1):(0.03-0.8):(0.2-4):(0.5-30), preferably Q:SiO2:GeO2:F:H2O = 0.15-4:0.2-0.9615:0.0385-0.8:0.2-4:0.5-30, more preferably Q:SiO2 The formula is:GeO2:F:H2O=0.25-3.5:0.333-0.9524:0.0476-0.667:0.35-3.5:1-25, further preferred is Q:SiO2:GeO2:F:H2O=0.3-2.5:0.5-0.9375:0.0625-0.5:0.4-2.5:2-20, further preferred is Q:SiO2:GeO2:F:H2O=0.35-1.5:0.6-0.909:0.091-0.4:0.45-2:3-15.

[0099] In this document, when a non-silicon and non-germanium element X is used to replace silicon and germanium atoms in the preparation method of the molecular sieve, a non-silicon and non-germanium element X source needs to be added to the mixture, preferably an oxide source of the non-silicon and non-germanium element X. As the oxide source, preferably at least one oxide source selected from boron oxide, alumina, gallium oxide, titanium oxide, zirconium oxide, hafnium oxide, tin oxide, zinc oxide, iron oxide, chromium oxide, and indium oxide is preferred. As the alumina source, at least one of aluminum hydroxide, sodium aluminate, aluminum salts, kaolin, and montmorillonite is included, but is not limited to. As the boron oxide source, at least one of boron oxide, borax, sodium metaborate, and boric acid is included, but is not limited to. As the tin oxide source, at least one of tin tetrachloride, stannous chloride, alkyltin, alkoxytin, and organostannate is included, but is not limited to. As the zirconium oxide source, at least one of zirconium salts (such as zirconium nitrate and zirconium sulfate), alkylzirconium, alkoxyzirconium, and organozirconate is included, but is not limited to. The titanium dioxide source includes, but is not limited to, one or more of tetraalkyl titanates (such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetran-n-butyl titanate), titanium tetrachloride, hexafluorotitanic acid, titanium sulfate, and their hydrolysis products. The gallium oxide source includes, but is not limited to, at least one of gallium nitrate, gallium oxide, gallium halide (such as gallium chloride, gallium bromide), gallium sulfate, gallium isopropoxide, gallium acetate, and gallium ethoxylate; the hafnium oxide source includes, but is not limited to, at least one of hafnium oxide, hafnium halide (such as hafnium chloride, hafnium bromide), hafnium sulfate, hafnium tert-butoxide, hafnium oxychloride, and hafnium ethoxylate; the zinc oxide source includes, but is not limited to, at least one of the group consisting of zinc oxide, zinc halide (such as zinc chloride), zinc acetate, basic zinc carbonate, zinc sulfate, zinc nitrate, zinc lactate, and zinc gluconate; the iron oxide source includes, but is not limited to, at least one of ferric sulfate, ferric nitrate, ferric halide (such as ferric chloride), ferrocene, and ferric citrate; the chromium oxide source includes, but is not limited to, at least one of chromium trioxide, chromium chloride, chromium nitrate, chromium acetate, and potassium chromium sulfate; the indium oxide source includes, but is not limited to, at least one of indium oxide, indium sulfate, indium halide (such as indium trichloride), and indium acetate.

[0100] In this document, in the method for preparing the molecular sieve, when in use, the oxide source (in the form of the corresponding oxide XO) m The molar ratio XO of the silicon source and the germanium source (calculated as SiO2+GeO2) to the silicon source and the germanium source (calculated as SiO2+GeO2) is... m / (SiO2+GeO2) is (0-0.2):1, preferably (0.01-0.01):1.

[0101] In this document, in the method for preparing the molecular sieve, after the crystallization is completed, the molecular sieve can be separated from the obtained reaction mixture as a product by any conventionally known separation method, thereby obtaining SCM-41 molecular sieve, also known as the synthetic form of SCM-41 molecular sieve. Examples of such separation methods include filtering, washing, and drying the obtained reaction mixture.

[0102] In this document, the filtration, washing, and drying processes in the preparation method of the molecular sieve can be performed in any manner conventionally known in the art. Specifically, for example, the filtration can be performed by simply filtering the obtained reaction mixture. For example, washing can be done using deionized water. The drying temperature can be, for example, 40 to 250°C, preferably 60 to 150°C, and the drying time can be, for example, 8 to 30 hours, preferably 10 to 20 hours. This drying can be carried out under normal pressure or under reduced pressure.

[0103] In this document, the molecular sieve preparation method may, as needed, be calcined to remove the organic template agent and any present moisture, thereby obtaining a calcined molecular sieve, also known as the calcined form of SCM-41 molecular sieve. The calcination can be carried out in any manner 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. Furthermore, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere.

[0104] In this document, the SCM-41 molecular sieve can be in any physical form, such as powder, granules, or molded form (e.g., strips, cloverleaf shapes, etc.). These physical forms can be obtained in any manner conventionally known in the art, without particular limitation.

[0105] In this document, the SCM-41 molecular sieve can be used in combination with other materials to obtain molecular sieve compositions. Examples of these other materials include, for example, active and inactive materials. Examples of active materials include, for example, synthetic zeolites and natural zeolites, while examples of inactive materials (generally referred to as binders) include, for example, clay, kaolin, silica gel, and alumina. These other materials can be used individually or in combination in any proportion. The amount of these other materials used can be directly referred to conventional amounts in the art and is not particularly limited.

[0106] In this document, the SCM-41 molecular sieve or the molecular sieve composition can be used as an adsorbent, for example, to separate at least one component from a mixture of multiple components in the gas or liquid phase. Thus, at least one component can be partially or substantially completely separated from a mixture of various components by contacting the mixture with the SCM-41 molecular sieve or the molecular sieve composition, selectively adsorbing this component.

[0107] In this document, the SCM-41 molecular sieve or the molecular sieve composition may also be used as a catalyst (or as its catalytically active component) directly or after undergoing the necessary treatments or transformations (such as ion exchange) conventionally performed on molecular sieves in the art. Therefore, in some embodiments, reactants (such as hydrocarbons) may be subjected to a predetermined reaction in the presence of the catalyst to obtain the target product.

[0108] The reagents used in the following examples are commercially available and of analytical grade.

[0109] The present invention will be further described in detail below with reference to the following specific embodiments. However, the scope of protection of the present invention is not limited to the following embodiments.

[0110] Example 1

[0111] 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 1.57 g of water. 1.2 g of germanium oxide was added, followed by the slow addition of 4.29 g of Ludox silica sol (40 wt% SiO2) under stirring. The mixture was stirred at room temperature for 4 hours. Finally, 1.5 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in an oven at 155 °C for 168 hours. The resulting solid was filtered, washed with distilled water, and dried at 100 °C to obtain the raw powder. The raw powder was then calcined in a muffle furnace at 550 °C for 5 hours to obtain the final product, SCM-41 molecular sieve.

[0112] The final product, SCM-41 molecular sieve, has a framework topology comprising [4] 6 ]、[4 4 0.6 2 ]、[4 2 0.5 4 ]、[4 2 0.5 4 0.6 2 ]、[4 7 0.5 6 0.6 9 .10 4 The natural splicing structure of ], see Figure 1 a; The framework topological minimal repeating unit of SCM-41 molecular sieve consists of 2 [4]6 ], 2 [4 4 0.6 2 ], 2 [4 2 0.5 4 ], 1 [4 2 0.5 4 0.6 2 ], 2 [4 7 0.5 6 0.6 9 .10 4 The structure is composed of natural splicing parts; see splicing method for details. Figure 1 b. Another framework topology of this SCM-41 molecular sieve includes [4 6 ]、[4 4 0.6 2 ]、[4 2 0.5 4 ]、[4 2 0.6 4 ]、[4 14 0.5 8 0.6 16 .10 8 Natural splicing structure, see Figure 2 a; The framework topological minimal repeating unit of SCM-41 molecular sieve consists of 2 [4] 6 ], 2 [4 4 0.6 2 ], 2 [4 2 0.5 4 ], 1 [4 2 0.6 4 ], 2 [4 14 0.5 8 0.6 16 .10 8 The structure is composed of natural splicing parts; see splicing method for details. Figure 2 b.

[0113] The SCM-41 molecular sieve has intersecting 10-membered ring-shaped open cylindrical channels along the

[010] and

[110] directions of the crystal, see [link to relevant documentation]. Figure 3 , Figure 4 The SCM-41 molecular sieve's 10-membered ring open channel has an elliptical planar projection, with the major axis of the elliptical pore being... minor axis is

[0114] The XRD pattern of the SCM-41 molecular sieve is as follows: Figure 5 As shown in Table 1, the spectral data are shown in Table 2-4; the parameters, analysis, and refinement results of the three-dimensional electron diffraction data of the original powder sample are shown in Table 2-4.

[0115] The SEM image of the SCM-41 molecular sieve is shown below. Figure 6 As shown, by Figure 6 It can be seen that SCM-41 molecular sieve is a plate-like crystal; the nitrogen adsorption-desorption isotherm is as follows: Figure 7 As shown, by Figure 7 It can be seen that SCM-41 molecular sieve has a type I isotherm and a specific surface area of ​​507 m². 2 / g, micropore volume is 0.19cm³ 3 / g. The composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0116] Table 1

[0117]

[0118] Table 2

[0119]

[0120]

[0121] Table 3

[0122]

[0123]

[0124] Table 4

[0125]

[0126]

[0127] Example 2

[0128] 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed thoroughly with 0.24 g of water. 0.7 g of germanium oxide was added, followed by the slow addition of 5 g of Ludox silica sol (40 wt% SiO2) under stirring. The mixture was stirred at room temperature for 4 hours. Finally, 3 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. The mixture was then transferred to a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 155°C oven for 192 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final product. The XRD pattern is shown below. Figure 8 As shown, by Figure 8 It can be seen that the product is SCM-41 molecular sieve, and the spectral data is shown in Table 5; the SEM images are shown below. Figure 9 As shown, by Figure 9 It can be seen that SCM-41 molecular sieve is a plate-like crystal; the nitrogen adsorption-desorption isotherm is as follows: Figure 10 As shown, by Figure 10 It can be seen that SCM-41 molecular sieve has a type I isotherm and a specific surface area of ​​414 m². 2 / g, micropore volume is 0.15cm³ 3 / g. The composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0129] Table 5

[0130]

[0131]

[0132] Example 3

[0133] 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed thoroughly with 2.65 g of water. 1.4 g of germanium oxide was added, followed by the slow addition of 4 g of Ludox silica sol (SiO2 40 wt%) 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. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 150°C oven for 144 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD pattern is consistent with... Figure 5 Similar. The composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0134] Example 4

[0135] 7.36 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 4.3 g of water. 0.84 g of germanium oxide was added, followed by the slow addition of 2.02 g of silica (SiO2 95 wt%) under stirring. 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. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 160°C oven for 120 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. XRD patterns are shown in Table 6, and the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0136] Table 6

[0137]

[0138]

[0139] Example 5

[0140] 9.82 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 0.7 g of water. 0.38 g of germanium oxide was added, followed by the slow addition of 3 g of Ludox silica sol (SiO2 40 wt%) and 1.04 g of silica (SiO2 95 wt%) under stirring. The mixture was stirred at room temperature for 4 hours. Finally, 0.051 g of the SCM-41 molecular sieve obtained in Example 1 was added as a seed crystal and 3 g of hydrofluoric acid (40 wt%). After stirring for another hour, the mixture was placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 165°C oven for 216 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD pattern is consistent with... Figure 5 Similarly, the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0141] Example 6

[0142] 7.85 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 0.6 g of water. 1.05 g of germanium oxide was added, followed by the slow addition of 4.5 g of Ludox silica sol (SiO2 40 wt%) under stirring. 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. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in an oven at 145 °C for 192 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD pattern is consistent with... Figure 5 Similarly, the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0143] Example 7

[0144] 5.89 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 0.6 g of water. 0.49 g of germanium oxide was added, followed by the slow addition of 3 g of Ludox silica sol (SiO2 40 wt%) and 0.96 g of silica fume (SiO2 95 wt%) under stirring. The mixture was stirred 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 the mixture was stirred for another hour. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 160°C oven for 192 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD pattern is consistent with... Figure 5 Similarly, the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0145] Example 8

[0146] 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed thoroughly with 3.1 g of water. Then, 1.2 g of germanium oxide and 0.204 g of titanium sulfate were added. 4.29 g of Ludox silica sol (SiO2 40wt%) was slowly added while stirring. The mixture was stirred at room temperature for 4 hours. Finally, 2 g of hydrofluoric acid (40wt%) was added, and stirring was continued for 1 hour. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 160°C oven for 168 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD pattern is consistent with... Figure 5 Similarly, the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0147] Example 9

[0148] 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed thoroughly with 0.55 g of water. 0.7 g of germanium oxide was added, followed by the slow addition of 0.34 g of Al2(SO4)3 solution (20 wt%) and 5 g of Ludox silica sol (SiO2 40 wt%) while stirring. The mixture was stirred at room temperature for 4 hours. Finally, 3 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 155°C oven for 192 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD pattern is consistent with... Figure 5 Similarly, the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0149] Example 10

[0150] 4.91 g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed thoroughly with 4.3 g of water. 1.2 g of germanium oxide was added, followed by the slow addition of 3.42 g of Al2(SO4)3 solution (20 wt%) and 4.29 g of Ludox silica sol (SiO2 40 wt%) under stirring. The mixture was stirred at room temperature for 4 hours. Finally, 2 g of hydrofluoric acid (40 wt%) was added, and stirring was continued for 1 hour. The mixture was then placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in a 155°C oven for 168 hours. The resulting solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD patterns are shown in Table 7, and the composition of the raw materials used to synthesize this molecular sieve is shown in Table 8.

[0151] Table 7

[0152]

[0153]

[0154] Table 8 Molar ratio composition of molecular sieve raw materials in the examples

[0155] project <![CDATA[SiO2 / GeO2]]> R / (Si+Ge) F / (Si+Ge) <![CDATA[H2O / (Si+Ge)]]> X X / (Si+Ge) Example 1 2.5 0.5 0.75 7 / / Example 2 5 0.5 1.5 7 / / Example 3 2 0.5 1 10.5 / / Example 4 4 0.75 1.5 8.5 / / Example 5 10 1 1.5 6 / / Example 6 3 0.8 1.6 8 / / Example 7 7.5 0.6 1.8 7.5 / / Example 8 2.5 0.5 1 9.5 Ti 0.025 Example 9 5 0.5 1.5 7.8 Al 0.01 Example 10 2.5 0.5 1 15 Al 0.1

[0156] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An SCM-41 molecular sieve, wherein the SCM-41 molecular sieve comprises SiO2 and GeO2, the molar ratio of SiO2 to GeO2 being (0.25-25):1, and the X-ray diffraction pattern of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the table below:

2. The SCM-41 molecular sieve according to claim 1, characterized in that, The X-ray diffraction pattern also includes the X-ray diffraction peaks shown in the table below:

3. The SCM-41 molecular sieve according to claim 2, characterized in that, The X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below:

4. The SCM-41 molecular sieve according to claim 1, characterized in that, The X-ray diffraction pattern of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the table below:

5. The SCM-41 molecular sieve according to claim 4, characterized in that, The X-ray diffraction pattern also includes the X-ray diffraction peaks shown in the table below:

6. The SCM-41 molecular sieve according to claim 5, characterized in that, The X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below.

7. The SCM-41 molecular sieve according to any one of claims 1-6, characterized in that, The SCM-41 molecular sieve satisfies at least one of the following conditions (a)-(h): (a) The framework topology of the SCM-41 molecular sieve includes [4 6 ]、[4 4 0.6 2 ]、[4 2 0.5 4 ]、[4 2 0.5 4 0.6 2 ]、[4 7 0.5 6 0.6 9 .10 4 The natural splicing structure; (b) The framework topological minimal repeating unit of the SCM-41 molecular sieve consists of 2 [4] 6 ], 2 [4 4 0.6 2 ], 2 [4 2 0.5 4 ], 1 [4 2 0.5 4 0.6 2 ], 2 [4 7 0.5 6 0.6 9 .10 4 Composed of naturally joined structural elements; (c) The framework topology of the SCM-41 molecular sieve includes [4 6 ]、[4 4 0.6 2 ]、[4 2 0.5 4 ]、[4 2 0.6 4 ]、[4 14 0.5 8 0.6 16 .10 8 The natural splicing structure; (d) The minimum repeating unit of the SCM-41 molecular sieve framework topology consists of 2 [4] 6 ], 2 [4 4 0.6 2 ], 2 [4 2 0.5 4 ], 1 [4 2 0.6 4 ], 2 [4 14 0.5 8 0.6 16 .10 8 Composed of naturally joined structural elements; (e) The SCM-41 molecular sieve has intersecting 10-membered ring-shaped open cylindrical channels along the [010] and [110] directions of the crystal; (f) The SCM-41 molecular sieve belongs to the monoclinic crystal system; (g) The specific surface area of ​​the SCM-41 molecular sieve is 250-1000 m². 2 / g; (h) The micropore volume of the SCM-41 molecular sieve is 0.1-0.4 cm³. 3 / g.

8. The SCM-41 molecular sieve according to claim 7, characterized in that, The planar projection of the 10-element ring-shaped open cylindrical channel is elliptical.

9. The SCM-41 molecular sieve according to claim 8, characterized in that, The major axis of the ellipse is 10. The SCM-41 molecular sieve according to claim 8, characterized in that, The major axis of the ellipse is 11. The SCM-41 molecular sieve according to claim 8, characterized in that, The major axis of the ellipse is 12. The SCM-41 molecular sieve according to claim 8, characterized in that, The minor axis of the ellipse is 13. The SCM-41 molecular sieve according to claim 8, characterized in that, The minor axis of the ellipse is 14. The SCM-41 molecular sieve according to claim 8, characterized in that, The minor axis of the ellipse is 15. The SCM-41 molecular sieve according to claim 7, characterized in that, The cell parameters of the SCM-41 molecular sieve include 16. The SCM-41 molecular sieve according to claim 15, characterized in that, 17. The SCM-41 molecular sieve according to claim 15, characterized in that, 18. The SCM-41 molecular sieve according to claim 7, characterized in that, The cell parameters of the SCM-41 molecular sieve include 19. The SCM-41 molecular sieve according to claim 18, characterized in that, 20. The SCM-41 molecular sieve according to claim 18, characterized in that, 21. The SCM-41 molecular sieve according to claim 7, characterized in that, The cell parameters of the SCM-41 molecular sieve include 22. The SCM-41 molecular sieve according to claim 21, characterized in that, 23. The SCM-41 molecular sieve according to claim 21, characterized in that, 24. The SCM-41 molecular sieve according to claim 7, characterized in that, The unit cell parameters of the SCM-41 molecular sieve include α = 90° and γ = 90°.

25. The SCM-41 molecular sieve according to claim 24, characterized in that, β＝96～106°。 26. The SCM-41 molecular sieve according to claim 24, characterized in that, β＝97～105°。 27. The SCM-41 molecular sieve according to claim 24, characterized in that, β＝98～104°。 28. The SCM-41 molecular sieve according to claim 7, characterized in that, The specific surface area of ​​the SCM-41 molecular sieve is 300-800 m². 2 / g.

29. The SCM-41 molecular sieve according to claim 7, characterized in that, The micropore volume of the SCM-41 molecular sieve is 0.12-0.35 cm³. 3 / g.

30. The SCM-41 molecular sieve according to any one of claims 1-6, characterized in that, The molar ratio of SiO2 to GeO2 is (0.5-20):

1.

31. The SCM-41 molecular sieve according to claim 30, characterized in that, The molar ratio of SiO2 to GeO2 is (1-15):

1.

32. The SCM-41 molecular sieve according to claim 30, characterized in that, The molar ratio of SiO2 to GeO2 is (1.5-10):

1.

33. The SCM-41 molecular sieve according to claim 30, characterized in that, The synthesized form of the SCM-41 molecular sieve has a schematic chemical composition as shown in the formula "kF·mQ·SiO2·1 / nGeO2·pH2O", where Q is an organic template agent. 0.25≤n≤25； 0.05≤k≤1.0； 0.01≤m≤1.0； 0.005≤p≤0.5。 34. The SCM-41 molecular sieve according to claim 33, characterized in that, The organic template agent is selected from substances containing 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol.

35. The SCM-41 molecular sieve according to claim 33, characterized in that, 0.5≤n≤20； 0.05≤k≤0.5； 0.02≤m≤0.5； 0.01≤p≤0.4。 36. The SCM-41 molecular sieve according to claim 33, characterized in that, 1≤n≤15； 0.1≤k≤0.5； 0.05≤m≤0.5； 0.01≤p≤0.3。 37. The SCM-41 molecular sieve according to claim 33, characterized in that, 1.5≤n≤10； 0.1≤k≤0.4； 0.05≤m≤0.3； 0.02≤p≤0.2。 38. The SCM-41 molecular sieve according to any one of claims 1-6, characterized in that, The SCM-41 molecular sieve also contains oxides of element X.

39. The SCM-41 molecular sieve according to claim 38, characterized in that, Element X is selected from at least one of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, and indium.

40. The SCM-41 molecular sieve according to claim 38, characterized in that, Element X is selected from aluminum and / or titanium.

41. The SCM-41 molecular sieve according to claim 38, characterized in that, The ratio of the sum of the molar contents of Si and Ge to the molar contents of X, based on the molar content of elements, is ≥5.

42. The SCM-41 molecular sieve according to claim 41, characterized in that, The ratio of the sum of the molar contents of Si and Ge elements to the molar contents of X element, based on the molar content of elements, is ≥10.

43. The SCM-41 molecular sieve according to claim 41, characterized in that, In terms of elemental molar content, the ratio of the sum of the molar contents of Si and Ge to the molar contents of X is 10-100.

44. A method for preparing SCM-41 molecular sieve, comprising the steps of mixing a silicon source, a germanium source, a fluorine source, an organic template agent Q, water and an optional X element source, and carrying out a crystallization reaction to obtain the SCM-41 molecular sieve, wherein the organic template agent Q comprises 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol; The molar ratio of the organic template agent Q, the silicon source, the germanium source, the fluorine source, and water, calculated as SiO2, GeO2, and F, is (0.15-4):(0.2-0.9615):(0.0385-0.8):(0.2-4):(0.5-30). With oxide XO m Based on SiO2 and GeO2, the ratio of the molar content of the X element source to the sum of the molar contents of the silicon source and the germanium source is (0-0.2):

1. The conditions for the crystallization reaction include: Crystallize at 100-200℃ for 24-360 hours.

45. The preparation method according to claim 44, characterized in that, The preparation method also includes a roasting step.

46. ​​The preparation method according to claim 45, characterized in that, The silicon source is selected from at least one of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite molecular sieve, and tetraethyl orthosilicate; and / or The germanium source is selected from at least one of germanium oxide, germanium nitrate, and tetraalkoxy germanium; and / or The fluorine source is selected from at least one of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride; and / or The X element source is selected from at least one of the following: boron source, aluminum source, gallium source, titanium source, zirconium source, hafnium source, tin source, zinc source, iron source, chromium source, and indium source; and / or The molar ratio of the organic template agent Q, the silicon source, the germanium source, the fluorine source, and water, calculated as SiO2, GeO2, and F, is (0.25-3.5):(0.333-0.9524):(0.0476-0.667):(0.35-3.5):(1-25); and / or With oxide XO m Based on SiO2 and GeO2, the ratio of the molar content of the X element source to the sum of the molar contents of the silicon source and the germanium source is (0-0.1):

1. and / or The conditions for the crystallization reaction include: crystallization at 110-190°C for 48-300 hours; and / or The roasting conditions include roasting at 300-750℃ for 1-10 hours.

47. The preparation method according to claim 46, characterized in that, The fluorine source is selected from hydrofluoric acid and / or ammonium fluoride; and / or The X element source is selected from at least one of the following: boron oxide source, aluminum oxide source, gallium oxide source, titanium oxide source, zirconium oxide source, hafnium oxide source, tin oxide source, zinc oxide source, iron oxide source, chromium oxide source, and indium oxide source; and / or The molar ratio of the organic template agent Q, the silicon source, the germanium source, the fluorine source, and water, calculated as SiO2, GeO2, and F, is (0.3-2.5):(0.5-0.9375):(0.0625-0.5):(0.4-2.5):(2-20); and / or With oxide XO m Based on SiO2 and GeO2, the ratio of the molar content of the X element source to the sum of the molar contents of the silicon source and the germanium source is (0.01-0.01):

1. and / or The conditions for the crystallization reaction include: crystallization at 120-180°C for 72-240 hours; and / or The roasting conditions include roasting at 400-600℃ for 3-6 hours.

48. The preparation method according to claim 46, characterized in that, The molar ratio of the organic template agent Q, the silicon source, the germanium source, the fluorine source and water, calculated as SiO2, GeO2 and F respectively, is more preferably (0.35-1.5):(0.6-0.909):(0.091-0.4):(0.45-2):(3-15).

49. A molecular sieve composition comprising the SCM-41 molecular sieve according to any one of claims 1-43 or the SCM-41 molecular sieve prepared by the preparation method according to any one of claims 44-48, and active and / or inactive materials.

50. The use of the SCM-41 molecular sieve according to any one of claims 1-43, or the SCM-41 molecular sieve prepared by the preparation method according to any one of claims 44-48, or the molecular sieve composition according to claim 49 as an adsorbent or catalyst.

Images