SCM-41 molecular sieve as well as preparation method and application thereof

Abstract

The invention relates to a novel SCM-41 molecular sieve as well as a preparation method and application thereof, and the SCM-41 molecular sieve has a unique X-ray diffraction pattern and has a good application prospect in the aspects of adsorption separation, ion exchange and catalytic conversion of organic compounds.

Description

Technical Field

[0001] The invention belongs to the technical field of molecular sieves, and specifically relates to an SCM-41 molecular sieve and a preparation method and application thereof, as well as an SCM-41 molecular sieve composition and application thereof. Background Art

[0002] Molecular sieves are an important class of microporous crystalline materials with regular and orderly molecular-scale pore structures, adjustable chemical composition, strong acidity and high hydrothermal stability. They are currently widely used in catalysis, adsorption and ion exchange. The excellent performance of molecular sieves is highly dependent on their framework structure. Therefore, the synthesis of molecular sieves with special framework structures has always been one of the most important research directions in the field of molecular sieves. At present, more than 250 molecular sieves with new framework structures have been found. The framework structure of molecular sieves is usually composed of coordinated tetrahedrons (TO4) connected by common vertices (generally oxygen atoms). Among them, the tetrahedrons in the framework structure of zeolite molecular sieves are SiO4 tetrahedrons and AlO4 tetrahedrons. The two types of tetrahedrons in zeolite molecular sieves can be replaced by other types of tetrahedrons to form molecular sieves or molecular sieve-like structures with different framework structures. For example, AlO4 tetrahedron can be replaced by GaO4 or ZnO4 tetrahedron, thus forming the framework of heteroatom molecular sieve together with SiO4 tetrahedron; Ge and Si have similar coordination properties and can also form tetrahedral coordination structure. Through the connection of GeO4 and SiO4, a large number of new germanium-containing molecular sieves or molecular sieve-like structures can be formed. So far, no material with the same X-ray diffraction crystal structure as SCM-41 molecular sieve has been found. Summary of the invention

[0003] The invention provides a SCM-41 molecular sieve with a novel structure and a preparation method and application thereof.

[0004] The first aspect of the present invention provides a SCM-41 molecular sieve, the X-ray diffraction spectrum of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the following table:

[0005]

[0006]

[0007] In some embodiments, the X-ray diffraction pattern further comprises the X-ray diffraction peaks shown in the following table:

[0008]

[0009] In some embodiments, the X-ray diffraction pattern further comprises X-ray diffraction peaks as shown in the following table:

[0010]

[0011] In some embodiments, the X-ray diffraction pattern of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the following table:

[0012]

[0013]

[0014] In some embodiments, the X-ray diffraction pattern further comprises the X-ray diffraction peaks shown in the following table:

[0015]

[0016] In some embodiments, the X-ray diffraction pattern further comprises X-ray diffraction peaks as shown in the following table,

[0017]

[0018] In some embodiments, the framework topology of the SCM-41 molecular sieve comprises [4 6 ]、[4 4 .6 2 ]、[4 2 .5 4 ]、[4 2 .5 4 .6 2 ]、[4 7 .5 6 .6 9 .10 4 ]Natural splicing structures, such as Figure 1 As shown in a.

[0019] In some embodiments, the SCM-41 molecular sieve has a minimal repeating unit of framework topology consisting of 2 [4 6 ], 2 [4 4 .6 2 ], 2 [4 2 .5 4 ]、1[4 2 .5 4 .6 2 ], 2 [4 7 .5 6 .6 9 .10 4 ]Natural splicing structure, such as Figure 1 As shown in b.

[0020] In some embodiments, the framework topology of the SCM-41 molecular sieve comprises [4 6 ]、[4 4.6 2 ]、[4 2 .5 4 ]、[4 2 .6 4 ]、[4 14 .5 8 .6 16 .10 8 ]Natural splicing structures, such as Figure 2 As shown in a.

[0021] In some embodiments, the SCM-41 molecular sieve has a minimal repeating unit of framework topology consisting of 2 [4 6 ], 2 [4 4 .6 2 ], 2 [4 2 .5 4 ]、1[4 2 .6 4 ], 2 [4 14 .5 8 .6 16 .10 8 ]Natural splicing structure, such as Figure 2 As shown in b.

[0022] In some embodiments, the SCM-41 molecular sieve has crossed 10-membered ring open straight cylindrical channels along the

[010] direction and the

[110] direction of the crystal.

[0023] In some embodiments, the plane projection of the SCM-41 molecular sieve 10-membered ring open straight cylindrical pore channel is an ellipse.

[0024] In some embodiments, the major axis of the ellipse is Best More preferred

[0025] In some embodiments, the minor axis of the ellipse is Best More preferred

[0026] In some embodiments, the SCM-41 molecular sieve is of monoclinic system.

[0027] In some embodiments, the unit cell parameters of the SCM-41 molecular sieve are Best More preferred

[0028] In some embodiments, the unit cell parameters of the SCM-41 molecular sieve are Best More preferred

[0029] In some embodiments, the unit cell parameters of the SCM-41 molecular sieve are Best More preferred

[0030] In some embodiments, the unit cell parameters of the SCM-41 molecular sieve are α=90° and γ=90°.

[0031] In some embodiments, the unit cell parameter of the SCM-41 molecular sieve is β=96-106°, preferably β=97-105°, and more preferably β=98-104°.

[0032] 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, preferably (0.5-20):1, more preferably (1-15):1, and further 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 therebetween.

[0033] In some embodiments, the SCM-41 molecular sieve has a schematic chemical composition as shown in the formula "SiO2·1 / nGeO2" after calcination, wherein the silicon-germanium molar ratio is 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and 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 therebetween.

[0034] In some embodiments, the SCM-41 molecular sieve has a schematic chemical composition as shown in the as-synthesized form of "kF·mQ·SiO2·1 / nGeO2·pH2O", where Q is an organic template, wherein:

[0035] 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, more preferably 1.5≤n≤10;

[0036] 0.05≤k≤1.0, preferably 0.05≤k≤0.5, more preferably 0.1≤k≤0.5, more preferably 0.1≤k≤0.4;

[0037] 0.01≤m≤1.0, preferably 0.02≤m≤0.5, more preferably 0.05≤m≤0.5, more preferably 0.05≤m≤0.3;

[0038] 0.005≤p≤0.5, preferably 0.01≤p≤0.4, more preferably 0.01≤p≤0.3, more preferably 0.02≤p≤0.2.

[0039] In some embodiments, the organic template is selected from a substance containing 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol. In some embodiments, the organic template is a substance containing 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, or 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, or 1-[Bis[3-(dimethylamino)propyl]amino]-2-propanol, and the structural formula is as follows:

[0040] The present invention selects the organic template agent with the specific structure to prepare the SCM-41 molecular sieve.

[0041] In some embodiments, the silicon and germanium elements in the SCM-41 molecular sieve may be substituted by X atoms, and the SCM-41 molecular sieve further comprises an oxide of element X. Preferably, element X is selected from at least one of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium, preferably aluminum and / or titanium.

[0042] In some embodiments, based on the molar content of the elements, the ratio of the sum of the molar content of the Si element and the Ge element to the molar content of the X element is ≥5, preferably ≥10, and more preferably 10 to 100. In some specific embodiments, based on the molar content of the elements, the ratio of the sum of the molar content of the Si element and the Ge element to the molar content of the X element can be 5, 10, 20, 40, 60, 80, 100, 150, 200 or any value therebetween.

[0043] In some embodiments, the specific surface area (BET method) of the SCM-41 molecular sieve is 250-1000m 2 / g, preferably 300-800m 2 / g.

[0044] In some embodiments, the micropore volume (t-plot method) of the SCM-41 molecular sieve is 0.1-0.4 cm 3 / g, preferably 0.12-0.35cm 3 / g.

[0045] The second aspect of the present invention provides a method for preparing an SCM-41 molecular sieve, comprising the steps of mixing a silicon source, a germanium source, a fluorine source, an organic template Q, water and an optional X element source, and performing a crystallization reaction to obtain the SCM-41 molecular sieve, wherein the organic template Q comprises 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol.

[0046] In some embodiments, the structural formula of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol is as follows:

[0047]

[0048] In some embodiments, the preparation method further comprises a calcination step.

[0049] 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.

[0050] In some embodiments, the germanium source is selected from at least one of germanium oxide, germanium nitrate, and tetraalkoxygermanium.

[0051] 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.

[0052] In some embodiments, the X element source is selected from at least one of 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, and an indium source; preferably selected from at least one of 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, and an indium oxide source.

[0053] In some embodiments, the molar ratio of the organic template Q, the silicon source (in terms of SiO2), the germanium source (in terms of GeO2), the fluorine source (in terms of 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).

[0054] In some embodiments, the X element source (in the form of oxide XO m The ratio of the molar content of the silicon source (in terms of SiO2 and GeO2) to the sum of the molar contents of the silicon source and the germanium source (in terms of SiO2 and GeO2) is (0-0.2):1, preferably (0-0.1):1, and more preferably (0.01-0.01):1.

[0055] In some embodiments, the crystallization reaction conditions include: crystallization at 100-200° C. for 24-360 hours, preferably crystallization at 110-190° C. for 48-300 hours, and more preferably crystallization at 120-180° C. for 72-240 hours.

[0056] In some embodiments, the calcination conditions include: calcination at 300-750° C. for 1-10 hours, preferably calcination at 400-600° C. for 3-6 hours.

[0057] The 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, and active materials and / or inactive materials.

[0058] In some embodiments, the active material includes but is not limited to synthetic zeolite and natural zeolite.

[0059] In some embodiments, the inactive material (generally referred to as a binder) includes but is not limited to clay, clay, silica gel, and alumina.

[0060] The fourth aspect of the present invention provides the use of the SCM-41 molecular sieve described in the first aspect, 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.

[0061] The present invention has the following beneficial effects:

[0062] (1) The present invention provides a brand new SCM-41 molecular sieve, whose framework structure has never been obtained in the art before;

[0063] (2) The SCM-41 molecular sieve of the present invention has a regular molecular size pore structure, strong acidity, ion exchange performance and high thermal stability;

[0064] (3) The SCM-41 molecular sieve preparation method of the present invention has simple synthesis steps, strong operability, and a wide synthesis range, which is easy to promote. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1A schematic diagram of the natural splicing of the framework topology structure of the SCM-41 molecular sieve obtained in Example 1 (a) and a schematic diagram of its composition (b).

[0066] Figure 2 A schematic diagram of the natural splicing of the framework topology structure of the SCM-41 molecular sieve obtained in Example 1 (a) and a schematic diagram of its composition (b).

[0067] Figure 3 These are projections of the framework structure of the SCM-41 molecular sieve obtained in Example 1 in different directions.

[0068] Figure 4 These are projections of the framework structure of the SCM-41 molecular sieve obtained in Example 1 in different directions.

[0069] Figure 5 This is the X-ray diffraction (XRD) pattern of the sample obtained in Example 1.

[0070] Figure 6 This is a scanning electron microscope (SEM) image of the sample obtained in Example 1.

[0071] Figure 7 This is the nitrogen adsorption-desorption isotherm of the sample obtained in Example 1.

[0072] Figure 8 This is the X-ray diffraction (XRD) pattern of the sample obtained in Example 2.

[0073] Fig. 9 This is a scanning electron microscope (SEM) image of the sample obtained in Example 2.

[0074] Fig.10 This is the nitrogen adsorption-desorption isotherm of the sample obtained in Example 2. DETAILED DESCRIPTION

[0075] For ease of understanding of the present invention, the present invention enumerates embodiment as follows. But those skilled in the art should understand that the embodiment is only to help understand the present invention, should not be regarded as specific limitation of the present invention. The endpoints and any value of the range disclosed in this article are not limited to the precise range or value, and these ranges or values ​​should be understood to include values ​​close to these ranges or values.

[0076] 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 meanings commonly understood by those skilled in the art. In the event of conflict, the definitions herein shall prevail.

[0077] In this article, the so-called specific surface area refers to the total area of ​​a sample per unit mass, including the internal surface area and the external surface area. Non-porous samples only have external surface area, such as silicate cement, some clay mineral powders, etc.; porous and porous samples have external surface area and internal surface area, such as asbestos fiber, diatomaceous earth and molecular sieves. The surface area of ​​pores with a pore size of less than 2nm in porous and porous samples 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 of ​​a sample per unit mass is the external specific surface area.

[0078] In this article, the so-called pore volume refers to the volume of pores per unit mass of porous materials. The so-called total pore volume refers to the volume of all pores per unit mass of molecular sieves (generally only pores with a pore diameter of less than 50nm are counted). The so-called micropore volume refers to the volume of all micropores per unit mass of molecular sieves (generally refers to pores with a pore diameter of less than 2nm).

[0079] In this article, the specific surface area, pore volume and micropore volume of the molecular sieve are determined by nitrogen physical adsorption, and the test conditions are 77K. The specific surface area is calculated using the BET (Brunauer-Emmett-Teller) method, with the point range of relative pressure p / p0=0.01~0.1; the total pore volume is calculated using the adsorption amount corresponding to the relative pressure p / p0=0.99; and the micropore volume is calculated using the t-plot method. The above test methods are all well known to those skilled in the art.

[0080] In this article, the structure of the molecular sieve is determined by an X-ray diffraction spectrum (XRD), and the X-ray diffraction spectrum (XRD) of the SCM-41 molecular sieve is determined by an X-ray powder diffractometer using a Cu-Kα ray source with a Kα1 wavelength of λ = 1.5405980 angstroms. Nickel filter.

[0081] In this article, in the XRD data of the molecular sieve, vw, w, m, s, vs represent the relative intensity of the diffraction peak, vw is very weak, w is weak, m is medium, s is strong, vs is very strong, which is well known to those skilled in the art. Generally speaking, vw is less than 5, w is less than 20; m is 20-40 (including 20, excluding 40); s is 40-70 (including 40, excluding 70); vs is greater than 70 (including 70).

[0082] In this paper, the framework topology natural splicing structure of the molecular sieve is obtained using TOPOS software, and the structural model is drawn using 3dt software; the unit cell parameters of the molecular sieve are obtained by powder XRD spectrum indexing and simulation software; the crystal structure of the molecular sieve is determined by three-dimensional electron diffraction data analysis and refinement, and the three-dimensional electron diffraction is automatically collected by the Instamatic software built into the JEOL JEM2100 transmission electron microscope. The structural analysis and refinement are performed by SHELXT and SHELXLE software respectively.

[0083] Herein, the SCM-41 molecular sieve has a schematic chemical composition I as shown in the formula "SiO2·1 / n GeO2". It is known that the molecular sieve sometimes contains a certain amount of water (especially just after synthesis), but the present invention does not consider it necessary to limit the amount of water, because the presence or absence of the water does not substantially affect the XRD spectrum of the molecular sieve. In view of this, the schematic chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, it is obvious that the schematic chemical composition I represents the skeleton chemical composition of the SCM-41 molecular sieve.

[0084] Herein, in the schematic chemical composition I, the silicon-germanium molar ratio is 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and more preferably 1.5≤n≤10.

[0085] In this article, just after synthesis, the molecular sieve may further contain organic matter (especially organic templates) and water in the composition, such as those filled in its pores. Therefore, the SCM-41 molecular sieve may also have a schematic chemical composition II as shown in the formula "kF·mQ·SiO2·1 / nGeO2·pH2O". Here, by roasting the molecular sieve having the schematic chemical composition II (sometimes also referred to as the molecular sieve precursor) to remove any organic templates and water present in its pores, a molecular sieve having the schematic chemical composition I can be obtained. In addition, the roasting can be carried out in any conventional manner known in the art, such as a roasting temperature generally from 300°C to 750°C, preferably from 400°C to 600°C, and a roasting time generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the roasting is generally carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere. In view of this, the schematic chemical composition I is sometimes also referred to as the schematic chemical composition after calcination, and the schematic chemical composition II is sometimes also referred to as the schematic chemical composition of the synthesized state.

[0086] Herein, in the schematic chemical composition II, the silicon-germanium molar ratio is 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, and more preferably 1.5≤n≤10.

[0087] Herein, in the schematic chemical composition II, F is fluorine, 0.05≤k≤1.0, preferably 0.05≤k≤0.5, more preferably 0.1≤k≤0.5, more preferably 0.1≤k≤0.4.

[0088] Herein, in the schematic chemical composition II, Q is an organic template, 0.01≤m≤1.0, preferably 0.02≤m≤0.5, more preferably 0.05≤m≤0.5, more preferably 0.05≤m≤0.3.

[0089] Herein, in the schematic chemical composition II, the organic template is 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, and the structural formula is shown below:

[0090]

[0091] Herein, in the schematic chemical composition II, 0.005≤p≤0.5, preferably 0.01≤p≤0.4, more preferably 0.01≤p≤0.3, more preferably 0.02≤p≤0.2.

[0092] In this article, in the SCM-41 molecular sieve, the framework silicon and germanium can be partially replaced by an element X other than silicon and germanium, and the replacement rate does not exceed 20%. Here, the parameter "replacement rate" is dimensionless. The non-silicon and germanium X element is selected from at least one of the group consisting of boron, aluminum, tin, zirconium and titanium, preferably selected from at least one of the group consisting of aluminum and titanium. Substitution rate = X / (Si+Ge)×100%, and the number of moles is used when calculating the substitution rate.

[0093] Herein, the SCM-41 molecular sieve can be synthesized by the following method, comprising the step of subjecting a mixture comprising a silicon source, a germanium source, a fluorine source, an organic template agent Q, water and an optional X element source (hereinafter collectively referred to as a mixture) to a crystallization reaction to obtain the molecular sieve.

[0094] Herein, in the method for preparing the molecular sieve, the organic template Q includes 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, and its structural formula is shown below:

[0095]

[0096] Herein, in the method for preparing the molecular sieve, the crystallization step can be carried out in any manner conventionally known in the art, such as a method of mixing the silicon source, the germanium source, the fluorine source, the organic template Q, water and an optional X element source in a predetermined ratio, and subjecting the obtained mixture to hydrothermal crystallization under the crystallization conditions, and optionally in the presence of stirring.

[0097] Herein, in the method for preparing the molecular sieve, as the silicon source, any silicon source conventionally used for this purpose in the art can be used, including but not limited to water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite molecular sieve, or tetraethyl orthosilicate, etc. These silicon sources can be used alone or in combination in a desired ratio.

[0098] Herein, in the method for preparing the molecular sieve, as the germanium source, any germanium source conventionally used for this purpose in the art can be used, including but not limited to germanium oxide, germanium nitrate and tetraalkoxygermanium.

[0099] Herein, in the method for preparing the molecular sieve, as the fluorine source, any fluorine source conventionally used for this purpose in the art can be used, including but not limited to fluoride or its aqueous solution, such as hydrofluoric acid, ammonium fluoride, sodium fluoride, potassium fluoride, especially hydrofluoric acid, ammonium fluoride, etc.

[0100] In some embodiments, in the preparation method of the molecular sieve, the molar ratio of the organic template Q, the silicon source (in terms of SiO2), the germanium source (in terms of GeO2), the fluorine source (in terms of 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 :GeO2:F:H2O=0.25-3.5:0.333-0.9524:0.0476-0.667:0.35-3.5:1-25, further preferred 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 Q:SiO2:GeO2:F:H2O=0.35-1.5:0.6-0.909:0.091-0.4:0.45-2:3-15.

[0101] In this article, in the preparation method of the molecular sieve, when non-silicon and germanium X elements are used to replace silicon and germanium atoms, it is necessary to add non-silicon and germanium X element sources to the mixture, preferably non-silicon and germanium X element oxide sources. As the oxide source, it is preferably selected from at least one oxide source 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; as the aluminum oxide source, it includes but is not limited to at least one of aluminum hydroxide, sodium aluminate, aluminum salt, kaolin and montmorillonite; as the boron oxide source, it includes but is not limited to at least one of boron oxide, borax, sodium metaborate and boric acid; as the tin oxide source, it includes but is not limited to at least one of tin tetrachloride, stannous chloride, alkyl tin, alkoxy tin and organic tin ester. As the zirconium oxide source, it includes but is not limited to at least one of zirconium salts (such as zirconium nitrate, zirconium sulfate), alkyl zirconium, alkoxy zirconium and organic zirconate. The titanium oxide source includes, but is not limited to, one or more of tetraalkyl titanates (such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra-n-butyl titanate), titanium tetrachloride, hexafluorotitanic acid, titanium sulfate, and hydrolyzates thereof. As the gallium oxide source, it 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 ethoxide; as the hafnium oxide source, it 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 ethoxide; as the zinc oxide source, it 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; as the iron oxide source, it includes but is not limited to at least one of ferric sulfate, ferric nitrate, iron halide (such as ferric chloride), ferrocene, and ferric citrate; as the chromium oxide source, it includes but is not limited to at least one of chromium trioxide, chromium chloride, chromium nitrate, chromium acetate, and potassium chromium sulfate; as the indium oxide source, it includes but is not limited to: at least one of indium oxide, indium sulfate, indium halide (such as indium chloride), and indium acetate.

[0102] In this article, in the preparation method of the molecular sieve, when used, the oxide source (in the form of the corresponding oxide XO m The molar ratio XO of the silicon source and the germanium source (in terms of SiO2+GeO2) is m / (SiO2+GeO2) is (0-0.2):1, preferably (0.01-0.01):1.

[0103] Herein, 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 SCM-41 molecular sieve in a synthesized state. As the separation method, for example, a method of filtering, washing and drying the obtained reaction mixture can be cited.

[0104] In this article, in the preparation method of the molecular sieve, the filtering, washing and drying can be carried out in any conventional manner known in the art. Specifically, as the filtering, for example, the obtained reaction mixture can be simply filtered. As the washing, for example, washing with deionized water can be cited. As the drying temperature, for example, it can be 40 to 250°C, preferably 60 to 150°C, and as the drying time, for example, it can be 8 to 30 hours, preferably 10 to 20 hours. The drying can be carried out at normal pressure or under reduced pressure.

[0105] In this article, in the preparation method of the molecular sieve, the molecular sieve obtained by crystallization can be calcined as needed to remove the organic template and possible moisture, etc., thereby obtaining the calcined molecular sieve, also known as the SCM-41 molecular sieve in the calcined form. The calcination can be carried out in any conventional manner known in the art, such as a calcination temperature of generally 300 to 800 ° C, preferably 400 to 650 ° C, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere.

[0106] Herein, the SCM-41 molecular sieve may be in any physical form, such as powder, granule or molded product (such as strip, clover, etc.). These physical forms may be obtained in any manner conventionally known in the art without particular limitation.

[0107] In this article, the SCM-41 molecular sieve can be used in combination with other materials to obtain a molecular sieve composition. As these other materials, for example, active materials and inactive materials can be cited. As the active material, for example, synthetic zeolite and natural zeolite can be cited, and as the inactive material (generally referred to as a binder), for example, clay, kaolin, silica gel and alumina can be cited. These other materials can be used alone or in combination with a variety of them in any proportion. As the amount of the other materials, the conventional amount used in the art can be directly referred to, without particular limitation.

[0108] In this article, 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 a gas phase or a liquid phase. Therefore, 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 to selectively adsorb the component.

[0109] Herein, the SCM-41 molecular sieve or the molecular sieve composition can also be used as a catalyst (or as its catalytically active component) directly or after necessary treatment or conversion (such as ion exchange, etc.) conventionally performed on the molecular sieve in the art. To this end, in some embodiments, for example, reactants (such as hydrocarbons) can be subjected to a predetermined reaction in the presence of the catalyst, and the target product can be obtained thereby.

[0110] The reagents used in the following examples are commercially available and of analytical grade.

[0111] The present invention is further described in detail below in conjunction with the following specific embodiments, and the protection content of the present invention is not limited to the following embodiments.

[0112] Example 1

[0113] 4.91g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 1.57g water, 1.2g germanium oxide was added, 4.29g Ludox silica sol (SiO2 40wt%) was slowly added under stirring, stirring was continued for 4h at room temperature, and finally 1.5g hydrofluoric acid (40wt%) was added, stirring was continued for 1 hour, and the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner, and placed in a 155℃ oven for crystallization for 168 hours. After the reaction, the solid was filtered, washed with distilled water, and dried at 100℃ to obtain the original powder solid, which was placed in a muffle furnace and calcined at 550℃ for 5 hours to obtain the final product SCM-41 molecular sieve.

[0114] The final product SCM-41 molecular sieve has a framework topology comprising [4 6 ]、[4 4 .6 2 ]、[4 2 .5 4 ]、[4 2 .5 4 .6 2 ]、[4 7 .5 6 .6 9 .10 4 ] for the natural splicing structure of Figure 1 a; The minimum repeating unit of the framework topology of SCM-41 molecular sieve consists of 2 [46 ], 2 [4 4 .6 2 ], 2 [4 2 .5 4 ]、1[4 2 .5 4 .6 2 ], 2 [4 7 .5 6 .6 9 .10 4 ]Natural splicing structure, splicing method see Figure 1 b. Another framework topology of the SCM-41 molecular sieve includes [4 6 ]、[4 4 .6 2 ]、[4 2 .5 4 ]、[4 2 .6 4 ]、[4 14 .5 8 .6 16 .10 8 ] Natural splicing structure, see Figure 2 a; The minimum repeating unit of the framework topology of SCM-41 molecular sieve consists of 2 [4 6 ], 2 [4 4 .6 2 ], 2 [4 2 .5 4 ]、1[4 2 .6 4 ], 2 [4 14 .5 8 .6 16 .10 8 ]Natural splicing structure, splicing method see Figure 2 b.

[0115] The SCM-41 molecular sieve has crossed 10-membered ring open straight cylindrical channels along the

[010] and

[110] directions of the crystal, see Figure 3 , Figure 4 The plane projection of the 10-membered ring opening channel of the SCM-41 molecular sieve is an ellipse, and the long axis of the ellipse is The short axis is

[0116] The XRD pattern of the SCM-41 molecular sieve is as follows Figure 5 The spectrum data are shown in Table 1; the three-dimensional electron diffraction data parameters, analysis and refinement results of the original powder sample are shown in Tables 2-4.

[0117] The SEM image of the SCM-41 molecular sieve is shown in 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 ​​507m 2 / g, micropore volume is 0.19cm 3 / g. The composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0118] Table 1

[0119]

[0120] Table 2

[0121]

[0122]

[0123] Table 3

[0124]

[0125]

[0126] Table 4

[0127]

[0128]

[0129] Example 2

[0130] 4.91g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 0.24g water, 0.7g germanium oxide was added, 5g Ludox silica sol (SiO2 40wt%) was slowly added under stirring, stirring was continued for 4h at room temperature, and finally 3g hydrofluoric acid (40wt%) was added, stirring was continued for 1 hour, and the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner, and placed in a 155°C oven for crystallization for 192 hours. The solid after the reaction was filtered, washed, dried, and calcined to obtain the final product, and the XRD spectrum was as follows: Figure 8 As shown by Figure 8 It can be seen that the product is SCM-41 molecular sieve, and the spectrum data are shown in Table 5; the SEM photos are shown in Fig. 9 As shown by Fig. 9 It can be seen that SCM-41 molecular sieve is a plate-like crystal; the nitrogen adsorption-desorption isotherm is as follows Fig.10 As shown by Fig.10 It can be seen that SCM-41 molecular sieve has a type I isotherm and a specific surface area of ​​414m 2 / g, micropore volume is 0.15cm 3 / g. The composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0131] Table 5

[0132]

[0133] Example 3

[0134] 4.91g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 2.65g water, 1.4g germanium oxide was added, 4g Ludox silica sol (SiO2 40wt%) was slowly added under stirring, stirring was continued for 4h at room temperature, and finally 4g ammonium fluoride solution (37wt%) was added. After stirring for 1 hour, the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner and placed in a 150℃ oven for crystallization for 144 hours. The solid after the reaction was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product, and the XRD spectrum was consistent with Figure 5 The composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0135] Example 4

[0136] 7.36g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 4.3g water, 0.84g germanium oxide was added, 2.02g white carbon black (SiO2 95wt%) was slowly added under stirring, stirring was continued for 4h at room temperature, and finally 3g hydrofluoric acid (40wt%) was added, stirring was continued for 1 hour, and the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner, and placed in a 160°C oven for crystallization for 120 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product. The XRD spectrum data are shown in Table 6, and the raw material composition of the synthesized molecular sieve is shown in Table 8.

[0137] Table 6

[0138]

[0139] Example 5

[0140] 9.82g of 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed evenly with 0.7g of water, and 0.38g of germanium oxide was added. 3g of Ludox silica sol (SiO2 40wt%) and 1.04g of white carbon black (SiO2 95wt%) were slowly added under stirring, and stirring was continued at room temperature for 4h. Finally, 0.051g of the SCM-41 molecular sieve obtained in Example 1 was added as a seed crystal and 3g of hydrofluoric acid (40wt%). After stirring for 1 hour, the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner and placed in a 165°C oven for crystallization for 216 hours. The solid after the reaction was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product, and the XRD spectrum was consistent with that of the solid. Figure 5 Similarly, the composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0141] Example 6

[0142] 7.85g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 0.6g water, 1.05g germanium oxide was added, 4.5g Ludox silica sol (SiO2 40wt%) was slowly added under stirring, and stirring was continued at room temperature for 4h, and finally 2.4g hydrofluoric acid (40wt%) and 1.6g ammonium fluoride solution (37wt%) were added. After stirring for 1 hour, the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner and placed in a 145°C oven for crystallization for 192 hours. The solid after the reaction was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product, and the XRD spectrum was consistent with that of the solid after the reaction. Figure 5 Similarly, the composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0143] Example 7

[0144] 5.89g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 0.6g water, 0.49g germanium oxide was added, 3g Ludox silica sol (SiO2 40wt%) and 0.96g white carbon black (SiO2 95wt%) were slowly added under stirring, and stirring was continued at room temperature for 4h, and finally 2.4g hydrofluoric acid (40wt%) and 2.4g ammonium fluoride solution (37wt%) were added, and stirring was continued for 1 hour, and the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner, and placed in a 160°C oven for crystallization for 192 hours. The solid after the reaction was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product, and the XRD spectrum was consistent with that of the solid after the reaction. Figure 5 Similarly, the composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0145] Example 8

[0146] 4.91g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 3.1g water, 1.2g germanium oxide and 0.204g titanium sulfate were added, 4.29g Ludox silica sol (SiO2 40wt%) was slowly added under stirring, and stirring was continued for 4h at room temperature, and finally 2g hydrofluoric acid (40wt%) was added, and stirring was continued for 1 hour, and the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner, and placed in a 160℃ oven for crystallization for 168 hours. The solid after reaction was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product, and the XRD spectrum was consistent with Figure 5 Similarly, the composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0147] Example 9

[0148] 4.91g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 0.55g water, 0.7g germanium oxide was added, 0.34g Al2(SO4)3 solution (20wt%) and 5g Ludox silica sol (SiO240wt%) were slowly added in sequence under stirring, stirring was continued for 4h at room temperature, and finally 3g hydrofluoric acid (40wt%) was added. After stirring for 1 hour, the above mixture was placed in a crystallization kettle with a polytetrafluoroethylene liner and placed in a 155°C oven for crystallization for 192 hours. The solid after the reaction was filtered, washed, dried, and calcined to obtain the final SCM-41 molecular sieve product, and the XRD spectrum was consistent with Figure 5 Similarly, the composition of the raw materials for synthesizing the molecular sieve is shown in Table 8.

[0149] Example 10

[0150] 4.91g 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol was mixed with 4.3g water, 1.2g germanium oxide was added, 3.42g Al2(SO4)3 solution (20wt%) and 4.29g Ludox silica sol (SiO240wt%) were slowly added in sequence under stirring, stirring was continued for 4h at room temperature, 2g hydrofluoric acid (40wt%) was finally added, stirring was continued for 1 hour, the mixture was charged into a crystallization kettle with polytetrafluoroethylene lining, and placed in a 155°C oven for crystallization for 168 hours. The solid after reaction was filtered, washed, dried and calcined to obtain the final SCM-41 molecular sieve product, the XRD spectrum data is shown in Table 7, and the raw material composition of the molecular sieve is shown in Table 8.

[0151] Table 7

[0152]

[0153]

[0154] Table 8 Example Molecular Sieve Raw Material Molecular Ratio Composition

[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 are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A SCM-41 molecular sieve, the X-ray diffraction spectrum of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the following table:

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

3. The SCM-41 molecular sieve according to claim 1 or 2, characterized in that: The X-ray diffraction spectrum of the SCM-41 molecular sieve has the X-ray diffraction peaks shown in the following table: Preferably, the X-ray diffraction pattern also includes the X-ray diffraction peaks shown in the following table: More preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks as shown in the following table, 4. The SCM-41 molecular sieve according to any one of claims 1 to 3, 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 comprises [4 6 ]、[4 4 .6 2 ]、[4 2 .5 4 ]、[4 2 .5 4 .6 2 ]、[4 7 .5 6 .6 9 .10 4 ]’s natural splicing structure; (b) The minimum repeating unit of the framework topology of the SCM-41 molecular sieve consists of 2 [4 6 ], 2 [4 4 .6 2 ], 2 [4 2 .5 4 ]、1[4 2 .5 4 .6 2 ], 2 [4 7 .5 6 .6 9 .10 4 ]Natural splicing structure; (c) The framework topology of the SCM-41 molecular sieve comprises [4 6 ]、[4 4 .6 2 ]、[4 2 .5 4 ]、[4 2 .6 4 ]、[4 14 .5 8 .6 16 .10 8 ]’s natural splicing structure; (d) The minimum repeating unit of the framework topology of the SCM-41 molecular sieve consists of 2 [4 6 ], 2 [4 4 .6 2 ], 2 [4 2 .5 4 ]、1[4 2 .6 4 ], 2 [4 14 .5 8 .6 16 .10 8 ]Natural splicing structure; (e) the SCM-41 molecular sieve has intersecting 10-membered ring open straight cylindrical channels along the [010] direction and the [110] direction of the crystal, Preferably, the plane projection of the 10-membered ring open straight cylindrical channel is an ellipse; More preferably, the major axis of the ellipse is Best More preferred More preferably, the minor axis of the ellipse is Best More preferred (f) the SCM-41 molecular sieve belongs to the monoclinic system; Preferably, the unit cell parameters of the SCM-41 molecular sieve include Best More preferred Preferably, the unit cell parameters of the SCM-41 molecular sieve include Best More preferred Preferably, the unit cell parameters of the SCM-41 molecular sieve include Best More preferred Preferably, the unit cell parameters of the SCM-41 molecular sieve include α=90°, γ=90°; Preferably, the unit cell parameter of the SCM-41 molecular sieve is β=96-106°, preferably β=97-105°, more preferably β=98-104°; (g) The specific surface area of ​​the SCM-41 molecular sieve is 250-1000m 2 / g, preferably 300-800m 2 / g; (h) The micropore volume of the SCM-41 molecular sieve is 0.1-0.4 cm 3 / g, preferably 0.12-0.35cm 3 / g.

5. The SCM-41 molecular sieve according to any one of claims 1 to 4, characterized in that: The SCM-41 molecular sieve comprises SiO2 and GeO2; Preferably, the molar ratio of SiO2 to GeO2 is (0.25-25):1, preferably (0.5-20):1, more preferably (1-15):1, and further preferably (1.5-10):1; Preferably, the SCM-41 molecular sieve in its synthesized state has a schematic chemical composition as shown in the formula "kF·mQ·SiO2·1 / nGeO2·pH2O", where Q is an organic template, wherein: 0.25≤n≤25, preferably 0.5≤n≤20, more preferably 1≤n≤15, more preferably 1.5≤n≤10; 0.05≤k≤1.0, preferably 0.05≤k≤0.5, more preferably 0.1≤k≤0.5, more preferably 0.1≤k≤0.4; 0.01≤m≤1.0, preferably 0.02≤m≤0.5, more preferably 0.05≤m≤0.5, more preferably 0.05≤m≤0.3; 0.005≤p≤0.5, preferably 0.01≤p≤0.4, more preferably 0.01≤p≤0.3, more preferably 0.02≤p≤0.2; Preferably, the organic template is selected from substances containing 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol.

6. The SCM-41 molecular sieve according to any one of claims 1 to 5, characterized in that The SCM-41 molecular sieve further comprises an oxide of element X; Preferably, the X element is selected from at least one of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium, preferably aluminum and / or titanium; Preferably, based on the molar content of the elements, the ratio of the sum of the molar content of Si element and Ge element to the molar content of X element is ≥5, preferably ≥10, and more preferably 10-100.

7. A method for preparing a 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 performing 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; Preferably, the preparation method further comprises a calcination step.

8. The preparation method according to claim 7, 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 tetraalkoxygermanium; and / or The fluorine source comprises at least one selected from hydrofluoric acid, ammonium fluoride, sodium fluoride and potassium fluoride, preferably selected from hydrofluoric acid and / or ammonium fluoride; and / or The X element source is selected from at least one of 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 and an indium source; preferably selected from at least one of 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 and an indium oxide source; and / or The molar ratio of the organic template Q, the silicon source (in terms of SiO2), the germanium source (in terms of GeO2), the fluorine source (in terms of F) and water is (0.15-4):(0.2-0.9615):(0.0385-0.8):(0.2-4):(0.5-30), preferably (0.25-3.5):(0.333-0.9524):(0.0476-0 .667):(0.35-3.5):(1-25), more preferably (0.3-2.5):(0.5-0.9375):(0.0625-0.5):(0.4-2.5):(2-20), further preferably (0.35-1.5):(0.6-0.909):(0.091-0.4):(0.45-2):(3-15); and / or The X element source (in the form of oxide XO m The ratio of the molar content of the silicon source (in terms of SiO2 and GeO2) to the molar content of the silicon source and the germanium source (in terms of SiO2 and GeO2) is (0-0.2):1, preferably (0-0.1):1, more preferably (0.01-0.01):1; and / or The conditions of the crystallization reaction include: crystallization at 100-200° C. for 24-360 hours, preferably crystallization at 110-190° C. for 48-300 hours, more preferably crystallization at 120-180° C. for 72-240 hours; and / or The calcination conditions include: calcination at 300-750° C. for 1-10 hours, preferably calcination at 400-600° C. for 3-6 hours.

9. A molecular sieve composition, comprising the SCM-41 molecular sieve according to any one of claims 1 to 6 or the SCM-41 molecular sieve prepared by the preparation method according to claim 7 or 8, and active materials and / or inactive materials.

10. Use of the SCM-41 molecular sieve according to any one of claims 1 to 6, or the SCM-41 molecular sieve prepared by the preparation method according to claim 7 or 8, or the molecular sieve composition according to claim 9 as an adsorbent or catalyst.

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