SCM-45 molecular sieve, preparation method therefor and use thereof

Abstract

Provided in the present invention are an SCM-45 molecular sieve, a preparation method therefor and the use thereof. The X-ray diffraction pattern of the SCM-45 molecular sieve comprises diffraction peaks at 2θvalues of 7.13° ± 0.30°, 8.10° ± 0.30°, 13.00° ± 0.30° and 19.41° ± 0.30°. The present SCM-45 molecular sieve comprises Si and optionally other elements in the framework thereof, and has a lamellar morphology, a high specific surface area, a large micropore volume, and excellent adsorption and catalytic properties.

Description

An SCM-45 molecular sieve, its preparation method and application Technical Field

[0001] This invention relates to the field of porous materials technology, specifically to an SCM-45 molecular sieve, its preparation method, and its application. Background Technology

[0002] Silicon-germanium molecular sieves are an important class of inorganic materials. Several well-studied silicate molecular sieves include UTL (US 7074385), BEC (US 6896869), and STW (Nature Mater., 2008, 7, 381-385). Silicon-germanium molecular sieves have distinct structural characteristics: 1) Most silicon-germanium molecular sieves contain double four-membered ring (D4R) structural units, and germanium preferentially enters the D4R; 2) The presence of double four-membered rings and double three-membered rings (D3R) structural units makes it easy for silicon-germanium molecular sieves to form ultra-large pores (pore openings larger than 12-membered rings) with low framework density; 3) The Ge-O bond is extremely unstable and easily breaks upon contact with water, resulting in generally poor hydrothermal stability of silicon-germanium molecular sieves.

[0003] Synthesizing novel silicon-germanium molecular sieves typically involves designing and using new organic structure-directing agents. However, since there is no strict one-to-one correspondence between structure-directing agents and the resulting molecular sieve structures, it is difficult to directionally design the molecular sieve structure. Removing some of the framework germanium elements can increase the silicon-germanium molar ratio of silicon-germanium molecular sieves, resulting in high-silicon molecular sieves. In the fields of catalysis, adsorption, separation, and energy storage, the exploration of new molecular sieves remains a persistent need. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide an SCM-45 molecular sieve, its preparation method, and its application.

[0005] In a first aspect, the present invention provides an SCM-45 molecular sieve, the X-ray diffraction pattern of which includes diffraction peaks with 2θ of 7.13°±0.30°, 8.10°±0.30°, 13.00°±0.30°, and 19.41°±0.30°.

[0006] Secondly, the present invention provides a method for preparing SCM-45 molecular sieve, comprising the following steps:

[0007] S10. A mixture of silicon source, germanium source, M source, fluorine source, structure directing agent and water is obtained to obtain a mixture (e.g., a mixed solution), wherein the M source is selected from at least one of the following group elements other than silicon and germanium: group IIIA, group IVA, group IVB, group IIB, group VIB, group VIIB, group IA, group IIA, group VIII, group VA or VB elements, as well as their elemental form, chloride, oxide, hydroxide, nitrate, sulfate, carbonate, acetate, isopropoxide or metaacid salt.

[0008] S20. The mixture (e.g., a liquid mixture) is subjected to a crystallization reaction to obtain a molecular sieve precursor;

[0009] S30. The molecular sieve precursor is brought into contact with the treatment liquid and subjected to treatment at a first temperature and a second temperature in sequence to obtain SCM-45 molecular sieve.

[0010] The treatment solution is selected from at least one of an acid solution, an alkaline solution, or an aqueous solution of an M' source, wherein the M' source in the aqueous solution is selected from at least one of a water-soluble compound of a Group IIIA element, Group IVA element, Group IVB element, Group IIB element, Group VIB element, Group VIIB element, Group IA element, Group IIA element, Group VIII element, Group VA element, or VB element.

[0011] The first temperature is 5℃-40℃, and the second temperature is 41℃-100℃.

[0012] Thirdly, the present invention provides a molecular sieve composition comprising the SCM-45 molecular sieve described in the first aspect of the present invention, and a binder.

[0013] Fourthly, the present invention provides the use of the SCM-45 molecular sieve described in the first aspect or the molecular sieve composition described in the third aspect of the present invention in catalytic reactions, adsorption or ion exchange.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1. This invention provides a novel SCM-45 molecular sieve.

[0016] 2. The SCM-45 molecular sieve of the present invention has a thin sheet structure, with a high specific surface area and a large micropore volume.

[0017] 3. The SCM-45 molecular sieve framework of the present invention contains Si and optional other elements, which can present different catalytic active centers to meet the needs of different reactions.

[0018] 4. The SCM-45 molecular sieve preparation method of the present invention has simple synthesis steps, strong operability, wide synthesis range, and is easy to promote.

[0019] 5. The SCM-45 molecular sieve framework preparation method of the present invention allows the SCM-45 molecular sieve framework to contain Si and other elements that can be selected within a certain range, and allows for the customization of catalytic active centers as needed. Attached Figure Description

[0020] The accompanying drawings are provided to further understand this application and form part of the specification. They are used together with the following detailed description to explain this application, but do not constitute a limitation thereof.

[0021] Figure 1 is a topological structure diagram of SCM-45 molecular sieve in one embodiment of the present invention;

[0022] Figure 2 is a schematic diagram of the contact between the molecular sieve precursor SCM-45P and the treatment liquid in one embodiment of the present invention.

[0023] Figure 3 is the X-ray diffraction (XRD) pattern of the precursor SCM-45P in Example 1.

[0024] Figure 4 shows the X-ray diffraction (XRD) pattern of the SCM-45 molecular sieve prepared in Example 1.

[0025] Figure 5 is a scanning electron microscope (SEM) image of the SCM-45 molecular sieve prepared in Example 1.

[0026] Figure 6 shows the nitrogen adsorption-desorption isotherm of the SCM-45 molecular sieve prepared in Example 1.

[0027] Figure 7 shows the X-ray diffraction (XRD) pattern of the SCM-45 molecular sieve prepared in Example 2.

[0028] Figure 8 is a scanning electron microscope (SEM) image of the SCM-45 molecular sieve prepared in Example 2.

[0029] Figure 9 shows the nitrogen adsorption-desorption isotherm of the SCM-45 molecular sieve prepared in Example 2.

[0030] Figure 10 shows the X-ray diffraction (XRD) pattern of the molecular sieve prepared in Comparative Example 1. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way.

[0032] The terminology used herein is for the purpose of describing particular exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "a," "an," and "the" as used herein are intended to include the plural forms as well. The terms "comprising," "including," "containing," and "having" are inclusive and thus describe the presence of the stated features, elements, compositions, steps, integers, operations, and / or components, but do not exclude the presence or inclusion of one or more other features, integers, steps, operations, elements, components, and / or sets thereof. Although the open-ended term "comprising" should be understood as a non-limiting term used to describe and claim the various embodiments described herein, in some respects it may instead be understood as a more restrictive and limiting term, such as "consisting of" or "essentially composed of." Thus, for any given embodiment describing a composition, material, component, element, feature, integer, operation, and / or process step, this disclosure also particularly includes embodiments consisting of or substantially consisting of such compositions, materials, components, elements, features, integers, operations, and / or process steps. In the case of "consisting of," the alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operations, and / or process steps. In the case of "essentially composed of," any additional compositions, materials, components, elements, features, integers, operations, and / or process steps that substantially affect the essential and novel characteristics are excluded from such embodiments. However, any compositions, materials, components, elements, features, integers, operations, and / or process steps that do not substantially affect the essential and novel characteristics may be included in the embodiments.

[0033] Any methods, procedures, and operations described herein should not be construed as necessarily requiring them to be performed in the specific order discussed or shown, unless explicitly stated otherwise. It should also be understood that additional or alternative steps may be used unless otherwise stated.

[0034] Although the terms first, second, third, etc., may be used herein to describe various steps, elements, components, regions, layers, and / or sections, these steps, elements, components, regions, layers, and / or sections should not be limited by these terms unless otherwise specified. These terms may be used only to distinguish one step, element, component, region, layer, or section from another. Unless clearly indicated by the context, terms such as "first," "second," and other numerical terms used herein do not imply order or sequence. Therefore, the first step, element, component, region, layer, or section discussed below may be referred to as the second step, element, component, region, layer, or section without departing from the teachings of the exemplary embodiments.

[0035] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0036] In this application, except where expressly stated, any matters or issues not mentioned herein shall be directly applicable to those known in the art without any modification. Furthermore, any implementation described herein may be freely combined with one or more other implementations described herein, and the resulting technical solutions or concepts shall be considered part of the original disclosure or original record of this application, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be clearly unreasonable.

[0037] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. The term "about" in this invention is defined as within ±10% of the stated numerical values, preferably ±5%, more preferably ±2%.

[0038] 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.

[0039] 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).

[0040] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0041] First aspect

[0042] In a first aspect, the present invention provides an SCM-45 molecular sieve, the X-ray diffraction pattern of which includes diffraction peaks with 2θ values ​​of 7.13°±0.30°, 8.10°±0.30°, 13.00°±0.30°, and 19.41°±0.30°. Preferably, the X-ray diffraction pattern of the SCM-45 molecular sieve includes diffraction peaks with 2θ values ​​of 7.13°±0.20°, 8.10°±0.20°, 13.00°±0.20°, and 19.41°±0.20°.

[0043] In some embodiments, the diffraction peak with a 2θ of 7.13° ± 0.30° is the strongest peak. Preferably, the diffraction peak with a 2θ of 7.13° ± 0.20° is the strongest peak.

[0044] In some embodiments, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes a diffraction peak with a 2θ of 26.17° ± 0.30°. Preferably, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes a diffraction peak with a 2θ of 26.17° ± 0.20°.

[0045] In some embodiments, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes one or more diffraction peaks with 2θ values ​​of 22.00°±0.30° and 27.22°±0.30°. Preferably, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes one or more diffraction peaks with 2θ values ​​of 22.00°±0.20° and 27.22°±0.20°.

[0046] In some embodiments, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes one or more diffraction peaks selected from 14.82°±0.30°, 16.03°±0.30°, 20.18°±0.30°, and 22.70°±0.30°. Preferably, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes one or more diffraction peaks selected from 14.82°±0.20°, 16.03°±0.20°, 20.18°±0.20°, and 22.70°±0.20°.

[0047] In some embodiments, the X-ray diffraction pattern of the SCM-45 molecular sieve includes the relative intensity characteristics of the diffraction peaks shown in Table A:

[0048] Table A

[0049] In some embodiments, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes the relative intensity characteristics of the X-ray diffraction peaks as shown in any one or more rows of Table B:

[0050] Table B

[0051] In some embodiments, the X-ray diffraction pattern of the SCM-45 molecular sieve includes the diffraction peak crystal plane intensities and relative intensity characteristics shown in Table C:

[0052] Table C

[0053] In some embodiments, the X-ray diffraction pattern further includes the interplanar spacing and relative intensity characteristics of the diffraction peaks shown in any one or more rows of Table D:

[0054] Table D

[0055] In this invention, in the X-ray diffraction pattern, vw, w, m, s, and vs represent the diffraction peak intensities, where vw indicates very weak, w indicates weak, m indicates moderate, s indicates strong, and vs indicates very strong. Generally speaking, vw indicates less than 5%, w indicates 5%-20%, m indicates 20%-40% (inclusive), s indicates 40%-70%, and vs indicates 70%-100% (inclusive).

[0056] Since the strength is affected by various factors, the data in the table represent the interplanar spacing of SCM-45 molecular sieve at 2θ (°) of 7.13 ± 0.3. The value is 12.39 ± 0.45, and the relative strength (%) (I / I0) × 100 is vs (70%-100%). And so on. Those skilled in the art are familiar with the representation methods of this table, and will not describe them in detail here.

[0057] In some embodiments, the molar ratio of SiO2 to GeO2 in the SCM-45 molecular sieve is ≥40, preferably ≥45.

[0058] Preferably, the SCM-45 molecular sieve further comprises MO. m / 2 Where M is a framework element excluding silicon and germanium, and m is the valence of element M, m = 1 to 7, where SiO2 and MO m / 2 The molar ratio is ≥20, preferably 50-200 (including the endpoints).

[0059] Preferably, the chemical composition of the SCM-45 molecular sieve is xSiO2·yGeO2·zMO.m / 2 Or x SiO2·y GeO2, where the molar ratio of SiO2 to GeO2 is x / y ≥ 40, preferably x / y ≥ 45, and in the presence of z, the ratio of SiO2 to MO m / 2 The molar ratio x / z ≥ 20, preferably 200 ≥ x / z ≥ 50. Where M is a framework element excluding silicon and germanium, and m is the valence of element M, m = 1 to 7. In the formula xSiO2·yGeO2, for example, x / y can be 40, 45, 50, 55, 60, 65, 70, 75, 80, 200, 400, 600, 800, 1000, +∞. When x / y = +∞, SCM-45 is a pure silicon molecular sieve. In the formula xSiO2·yGeO2·zMO m / 2 The same applies to x / y as described above. In the formula x SiO2·y GeO2·z MO m / 2 In this context, x / z can be, for example, 20, 30, 50, 100, 150, 200, 300, 400, 500, 600, 800, 1000, or +∞. When x / z = +∞ and x / y = +∞, the SCM-45 molecular sieve is a pure silicon molecular sieve. In some embodiments, 200 ≥ x / z ≥ 50. In the context of this invention, the framework elements of a molecular sieve mainly refer to the elements that constitute the crystal framework structure of the molecular sieve.

[0060] In some embodiments, the framework element M of the SCM-45 molecular sieve, excluding silicon and germanium, is selected from at least one of Group IIIA, Group IVA, Group IVB, Group IIB, Group VIB, Group VIIB, Group IA, Group IIA, Group VIII, Group VA, or Group VB elements, excluding silicon and germanium. Preferably, it is selected from at least one of aluminum, boron, gallium, indium, tin, titanium, zirconium, hafnium, zinc, chromium, manganese, lithium, beryllium, magnesium, iron, phosphorus, vanadium, cobalt, nickel, arsenic, or antimony.

[0061] The oxidation state of element M is m, where m = 1 to 7, taking the integer part. For example, when M is lithium, its oxidation state is +1, m = 1; when M is magnesium, its oxidation state is +2, m = 2; when M is aluminum, its oxidation state is +3, m = 3; when M is tin, its oxidation state can be +4, m = 4; when M is vanadium, its oxidation state can be +5, m = 5; when M is chromium, its oxidation state can be +6, m = 6; and when M is manganese, its oxidation state can be +7, m = 7.

[0062] This invention generates different catalytic active centers in high-silicon SCM-45 molecular sieves by introducing a non-silicon framework element M, which can meet the needs of different catalytic reactions.

[0063] In some embodiments, the SCM-45 molecular sieve comprises a plate-like crystal morphology.

[0064] In some embodiments, the thickness of the SCM-45 molecular sieve is 20 to 500 nm, for example, 20 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm or any value between them, preferably 20 to 100 nm.

[0065] In some embodiments, the specific surface area of ​​the SCM-45 molecular sieve is greater than 350 m². 2 / g. In some embodiments, the specific surface area of ​​the SCM-45 molecular sieve is 370-800 m². 2 / g, for example, 400m 2 / g、430m 2 / g、450m 2 / g、470m 2 / g、490m 2 / g、510m 2 / g、550m 2 / g、600m 2 / g、650m 2 / g、700m 2 / g、750m 2 / g、800m 2 / g or any value between them. In some embodiments, the specific surface area of ​​the SCM-45 molecular sieve is 400-700 m². 2 / g. In some embodiments, the specific surface area of ​​the SCM-45 molecular sieve is 400-550 m². 2 / g.

[0066] In some embodiments, the micropore volume of the SCM-45 molecular sieve is greater than 0.14 cm³. 3 / g. In some embodiments, the micropore volume of the SCM-45 molecular sieve is 0.15-0.5 cm³. 3 / g, for example, 0.15cm 3 / g, 0.16cm 3 / g, 0.17cm 3 / g, 0.18cm 3 / g, 0.19cm 3 / g, 0.20cm 3 / g, 0.22cm 3 / g, 0.24cm 3 / g, 0.26cm 3 / g, 0.35cm 3 / g, 0.4cm 3 / g, 0.45cm 3 / g, 0.5cm3 / g or any value between them. In some embodiments, the micropore volume of the SCM-45 molecular sieve is 0.15-0.35 cm³. 3 / g. In some embodiments, the micropore volume of the SCM-45 molecular sieve is 0.15-0.25 cm³. 3 / g. In the context of this invention, micropore volume is also referred to as micropore capacity.

[0067] In some embodiments, the SCM-45 molecular sieve includes a layered structure and interlayer connecting units, wherein the interlayer connecting units include single four-membered rings and double four-membered rings; preferably, the molar ratio of the single four-membered rings and the double four-membered rings is 1:2-2:1, for example, 1:2, 1:1.5, 1:1, 1.5:1, 2:1 or any value between them.

[0068] In this invention, the SCM-45 molecular sieve has a dense, silica-rich layer. XRD analysis shows that the interlayer connecting units include both single-quaternary rings and double-quaternary rings, with a molar ratio of approximately 1:1, as shown in Figure 1.

[0069] The SCM-45 molecular sieve of this invention has a framework comprising Si and optional other elements, which can present different catalytic active centers to meet the needs of different reactions. For example, the SCM-45 molecular sieve framework of this invention can contain Si and Al, the latter acting as an acidic active site in catalytic reactions. Simultaneously, the SCM-45 molecular sieve of this invention has a stable framework structure and an adjustable Si-Al ratio, enabling it to function more stably in different catalytic reactions. Without containing elements other than Si, the SCM-45 molecular sieve of this invention is suitable for separation applications.

[0070] Second aspect

[0071] Secondly, the present invention provides a method for preparing SCM-45 molecular sieve, comprising the following steps:

[0072] S10, a mixture of silicon source, germanium source, optional additional framework element M source, fluorine source, structure directing agent and water, is obtained to obtain a mixture (e.g., a mixed solution);

[0073] S20. The mixture (e.g., a liquid mixture) is subjected to a crystallization reaction to obtain a molecular sieve precursor;

[0074] S30. The molecular sieve precursor is brought into contact with the treatment liquid and subjected to treatment at a first temperature and a second temperature in sequence to obtain SCM-45 molecular sieve.

[0075] The treatment solution is selected from at least one of an acid solution, an alkaline solution, or an aqueous solution of an additional framework element M' source.

[0076] The first temperature is 5℃-40℃; the second temperature is 41℃-100℃.

[0077] The present invention does not impose any particular limitation on the order of addition in step S10 of the method for preparing the SCM-45 molecular sieve precursor. For example, the germanium source can be mixed with the structure directing agent and water first, and then the optional additional framework element M source and silicon source can be added in sequence, followed by the addition of the fluorine source to obtain the mixture (e.g., a mixed solution).

[0078] In some embodiments, the molar number of the silicon source is SiO2, the molar number of the germanium source is GeO2, and the M source is an oxide MO. m / 2 The fluorine source is expressed as F. In the mixture (e.g., a liquid mixture), the molar ratio of SiO2 to GeO2 is (2 to 10):1, for example, 2:1, 4:1, 5:1, 7.5:1, 10:1 or any value between them.

[0079] In some embodiments, the molar number of the silicon source is SiO2, the molar number of the germanium source is GeO2, and the molar number of the M source is MO. m / 2 The sum of the molar numbers of SiO2 and GeO2 in the mixture (e.g., the liquid mixture) is calculated to be equal to the molar number of MO. m / 2 The ratio of the number of moles is (15 to 30):1, for example, 15:1, 17.5:1, 20:1, 22.5:1, 25:1, 27.5:1, 30:1 or any value between them.

[0080] In some embodiments, the number of moles of silicon source is SiO2 and the number of moles of germanium source is GeO2. In the mixture (e.g., a liquid mixture), for simplicity, in some cases the sum of the number of moles of SiO2 and GeO2 is normalized to 1.

[0081] In some embodiments, the molar number of the silicon source is SiO2, the molar number of the germanium source is GeO2, and the molar number of the fluorine source is F. In the mixture (e.g., a liquid mixture), the molar ratio of the sum of the molar numbers of SiO2 and GeO2 to F is 1:(0.1-1), for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1; preferably 1:0.5.

[0082] In some embodiments, the molar number of the silicon source is SiO2, the molar number of the germanium source is GeO2, and the molar ratio of the sum of the molar numbers of SiO2 and GeO2 to the molar number of the structure directing agent in the mixture (e.g., a mixed liquid) is 1:(0.1-1), for example 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1; preferably 1:0.5.

[0083] In some embodiments, the mixture (e.g., a liquid mixture) contains silicon source in moles of SiO2 and germanium source in moles of GeO2. The sum of the moles of SiO2 and GeO2 in the mixture (e.g., a liquid mixture) has a molar ratio of water to water of 1:(12.5-25), for example, 1:12.5, 1:14, 1:16, 1:18, 1:20, 1:25 or any value between them.

[0084] In some preferred embodiments, the mixture (e.g., a liquid mixture) contains a structure-directing agent, SiO2, GeO2, and MO. m / 2 The molar ratio of F to water is 0.5:(0.667-0.909):(0.091-0.333):(0.0333-0.0667):0.5:(12.5-25).

[0085] In some embodiments, the silicon source is selected from at least one group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite molecular sieve, and tetraalkoxysilane.

[0086] In some embodiments, the germanium source is selected from at least one of germanium oxide, germanium nitrate, and tetraalkoxy germanium.

[0087] In some embodiments, the M source is selected from at least one of the following group elements other than silicon and germanium: group IIIA, group IVA, group IVB, group IIB, group VIB, group VIIB, group IA, group IIA, group VIII, group VA, or group VB elements, as well as their elemental forms, chlorides, oxides, hydroxides, nitrates, sulfates, carbonates, acetates, isopropoxides, or metaacids.

[0088] In some preferred embodiments, the M source is selected from at least one of the following: elemental form, chloride, oxide, hydroxide, nitrate, sulfate, carbonate, acetate, isopropoxide, or metaacid salt of aluminum, boron, gallium, indium, tin, titanium, zirconium, hafnium, zinc, chromium, manganese, lithium, beryllium, magnesium, iron, phosphorus, vanadium, cobalt, nickel, arsenic, or antimony. In some more preferred embodiments, the M source is selected from at least one of the following: elemental form, chloride, oxide, hydroxide, nitrate, sulfate, carbonate, acetate, isopropoxide, or metaacid salt of aluminum.

[0089] In some further preferred embodiments, the M source is selected from at least one of aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum chloride, boehmite, alumina, aluminum hydroxide, silica-alumina zeolite molecular sieve, aluminum carbonate, elemental aluminum, aluminum isopropoxide, and aluminum acetate.

[0090] In some embodiments, the fluorine source is selected from at least one of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, preferably at least one of hydrofluoric acid and ammonium fluoride.

[0091] In some embodiments, the structure directing agent is selected from those containing 1,1,3,5-tetraalkylpiperidine onium ions; preferably, the structure directing agent is 1,1,3,5-tetramethylpiperidine hydroxide.

[0092] The crystallization reaction described in this invention can be carried out under dynamic or static conditions. In this invention, the results of static and dynamic crystallization are essentially the same; therefore, the embodiments of this invention do not specifically describe static or dynamic conditions.

[0093] In some embodiments, the temperature of the crystallization reaction is 100-200°C, for example 100°C, 120°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or any value between them.

[0094] In some embodiments, the temperature of the crystallization reaction is 110-190°C, more preferably 155-175°C.

[0095] In some embodiments, the crystallization reaction time is 72-600 hours, for example, 80 hours, 100 hours, 140 hours, 180 hours, 220 hours, 240 hours, 280 hours, 320 hours, 360 hours, or any value between them. The crystallization reaction time is preferably 96-480 hours, more preferably 120-360 hours.

[0096] In some embodiments, the crystallization reaction is carried out in an autoclave. In a preferred embodiment, the crystallization reaction is carried out in a crystallization autoclave lined with polytetrafluoroethylene.

[0097] According to some embodiments, the preparation method of the present invention further includes step S25 between steps S20 and S30: post-processing the molecular sieve precursor, the post-processing including solid-liquid separation, washing, drying, and calcination. Preferably, the solid-liquid separation is performed by filtration. Preferably, the washing is performed once or multiple times with water.

[0098] After the crystallization step described in this invention is completed, the molecular sieve can be separated from the obtained reaction mixture by any conventionally known separation method. Examples of such separation methods include filtration or centrifugation of the obtained reaction mixture. Filtration and centrifugation can be performed in any manner conventionally known in the art. Specifically, for example, filtration can be performed by simply vacuum filtering the obtained reaction mixture. Washing and drying in this invention can be performed in any manner conventionally known in the art. Specifically, for example, washing can be performed using deionized water. For example, the drying temperature can be 40-250°C, preferably 60-150°C, and the drying time can be 1-30 hours, preferably 8-30 hours, more preferably 10-20 hours. This drying can be performed under normal pressure or under reduced pressure. The present invention involves calcining the molecular sieve precursor to remove the structure-directing agent and any present moisture. The calcination can be carried out in any manner conventionally known in the art; for example, the calcination temperature is generally 300-800°C, preferably 400-650°C, and the calcination time is generally 1-10 hours, preferably 3-6 hours. Furthermore, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere.

[0099] According to some embodiments, the molecular sieve precursor has an IWV topology. The molecular sieve precursor of the present invention can be named SCM-45P. Its framework can be considered as consisting of a dense silicon-rich layer in the bc plane and germanium-rich double-quaternary ring structural units connecting the layers along the a-axis. SCM-45 can be considered a derivative structure of SCM-45P. Compared with SCM-45P, the dense silicon-rich layer of SCM-45 remains unchanged, but the connecting units between the layers change from double-quaternary rings to single-quaternary rings and double-quaternary rings connected together. The molar ratio of single-quaternary rings to double-quaternary rings is 1:2-2:1, preferably about 1:1.

[0100] According to some embodiments, in step S30 of the preparation method of the present invention, the precursor is treated at a first temperature, and the Ge-O bond of the germanium-rich double four-membered ring in the interlayer breaks, causing the double four-membered ring to be removed from the framework; then, after a second temperature treatment, silicon atoms on the solution phase or silicon-rich layer are reinserted into the interlayer to form interlayer connections between single four-membered rings and double four-membered rings, and finally SCM-45 molecular sieve is obtained.

[0101] In some embodiments, the first temperature in step S30 of the preparation method is 5°C-40°C; for example, it is 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or any value between them;

[0102] In some embodiments, the duration of the first temperature treatment is 5 min to 5 h; for example, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 2 h, 3 h, 4 h, 5 h or any value between them, preferably 10 to 30 minutes.

[0103] In some embodiments, the second temperature is 41°C-100°C; for example, it is 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 75°C, 90°C, 95°C, 100°C or any value between them.

[0104] In some embodiments, the molecular sieve precursor contains 4 < Si / Ge ≤ 5.5, and when the second temperature is 41℃-55℃, the treatment time at the second temperature is ≥ 10.5h, for example, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h or any value between them or a range of any two of them, for example, 11-20h.

[0105] In some embodiments, the molecular sieve precursor contains 4 < Si / Ge ≤ 5.5, and when the second temperature is 56℃-70℃, the second temperature treatment time is ≥ 8.5h, for example 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h or any value between them or a range of any two of them, for example 9-15h.

[0106] In some embodiments, the molecular sieve precursor contains 4 < Si / Ge ≤ 5.5, and when the second temperature is 71℃-85℃, the treatment time at the second temperature is ≥ 6.5h, for example 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or any value between them or a range of any two of them, for example 7-13h.

[0107] In some embodiments, when the molecular sieve precursor has 4 < Si / Ge ≤ 5.5, and the second temperature is 86℃-100℃, the second temperature treatment time is ≥ 4.5h, for example 5h, 6h, 7h, 8h, 9h, 10h, 11h or any value between them or a range of any two of them, for example 5-10h.

[0108] In some embodiments, the molecular sieve precursor contains 5.5 < Si / Ge ≤ 7, and when the second temperature is 41℃-55℃, the second temperature treatment time is 5-9 hours; and / or

[0109] In some embodiments, the molecular sieve precursor contains 5.5 < Si / Ge ≤ 7, and when the second temperature is 56℃-70℃, the second temperature treatment time is 80 min-7 h.

[0110] In some embodiments, the molecular sieve precursor contains 5.5 < Si / Ge ≤ 7, and when the second temperature is 71℃-85℃, the second temperature treatment time is 60 min-5 h.

[0111] In some embodiments, the molecular sieve precursor contains 5.5 < Si / Ge ≤ 7, and when the second temperature is 86℃-100℃, the second temperature treatment time is 30 min-3 h.

[0112] In some embodiments, the Si / Ge ratio in the molecular sieve precursor is greater than 7, and when the second temperature is 41°C-55°C, the treatment time at the second temperature is 3.5-7 hours.

[0113] In some embodiments, the Si / Ge ratio in the molecular sieve precursor is greater than 7, and when the second temperature is 56°C-70°C, the treatment time at the second temperature is 1.5-5 hours.

[0114] In some embodiments, the Si / Ge ratio in the molecular sieve precursor is greater than 7, and when the second temperature is 71°C-85°C, the treatment time at the second temperature is 1-3.5 h.

[0115] In some embodiments, the Si / Ge ratio in the molecular sieve precursor is greater than 7, and when the second temperature is 86°C-100°C, the second temperature treatment time is 0.5-3 hours.

[0116] In the above embodiments, when the Si / Ge ratio in the molecular sieve precursor is greater than 7, the Si / Ge ratio of the molecular sieve precursor can be, for example, 7.5, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or any value between them or a range of any two of them, such as 7.5-20.

[0117] The contact method between the molecular sieve precursor and the treatment liquid in this invention can be direct contact or indirect contact. Direct contact generally refers to immersing the molecular sieve precursor in the treatment liquid and allowing it to react by standing or stirring. Indirect contact generally refers to placing the molecular sieve precursor above the treatment liquid, where the vapors evaporating from the treatment liquid react with the molecular sieve precursor, as shown in Figure 2.

[0118] In this invention, the molecular sieve precursor SCM-45P has an IWV topology, and its framework can be considered as consisting of a dense silicon-rich layer in the bc plane and germanium-rich double four-membered ring structural units connecting the layers along the a-axis. The SCM-45 molecular sieve can be considered a derivative structure of SCM-45P. Compared to SCM-45P, the dense silicon-rich layer of SCM-45 remains unchanged, but the interlayer connecting units change from double four-membered rings to a combination of single four-membered rings and double four-membered rings, with a molar ratio of approximately 1:1.

[0119] In some embodiments, the mass ratio of the treatment liquid to the molecular sieve precursor is 20-300, for example, 50, 100, 150, 200, 250, 300 or any value between them.

[0120] In some embodiments, the mass ratio of the treatment liquid to the molecular sieve precursor is 50-200.

[0121] In some embodiments, the treatment solution is selected from at least one of an acid solution, an alkaline solution, or an aqueous solution of an additional skeletal element M' source.

[0122] In some embodiments, the acid solution is selected from at least one of aqueous HCl solution, alcoholic HCl solution, aqueous H2SO4 solution, aqueous HNO3 solution, and acetic acid solution, preferably aqueous HCl solution.

[0123] In some embodiments, the HCl alcohol solution may include, for example, a methanol solution of HCl, an ethanol solution of HCl, or an isopropanol solution of HCl.

[0124] In some embodiments, the concentration of the acid solution is 0.01-20M, for example, 0.01M, 0.1M, 1M, 2M, 3M, 6M, 9M, 12M, 20M or any value between them or a range of any two of them, for example, 0.1-12M.

[0125] In some embodiments, the concentration of the acid solution is 0.01-14M.

[0126] In some embodiments, the concentration of the HCl aqueous solution may be, for example, 0.01M, 0.1M, 1M, 2M, 3M, 6M, 9M, 12M, or any value between them or a range of any two of them, such as 0.1-12M.

[0127] In some embodiments, the concentration of the HNO3 aqueous solution may be, for example, 0.01M, 0.1M, 1M, 2M, 3M, 6M, 8M, 10M, 12M, 14M, or any value between them or a range of any two of them, such as 0.1-12M.

[0128] In some embodiments, the alkaline solution is an aqueous ammonia solution.

[0129] In some embodiments, the concentration of the alkaline solution is 0.1-30 wt%, for example, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 25 wt%, or any value between them.

[0130] In some embodiments, the concentration of the alkaline solution is 0.5-25 wt%.

[0131] In some embodiments, the concentration of the ammonia solution can be 0.5wt%, 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 25wt%, etc.

[0132] When the treatment solution is an aqueous solution containing an additional framework element M' source, the M' source will enter the molecular sieve framework and form a molecular sieve with the silicon source, germanium source, and M source having the following general formula: xSiO2·yGeO2·zMO m / 2 Where M is a framework element other than silicon, m is the valence of element M, and m = 1 to 7. Specifically, SiO2 and MO... m / 2 The molar ratio is x / z, x / z≥20, at this time, MO m / 2 M in M ​​includes elements from both the source M and the source M'.

[0133] In some embodiments, the M' source in the aqueous solution of the M' source is selected from at least one water-soluble compound of a group IIIA, IVA, IVB, IIB, VIB, VIIB, IA, IIA, VIII, VA, or VB element.

[0134] In some embodiments, the M' source in the aqueous solution of the M' source is selected from at least one of water-soluble compounds of aluminum, boron, gallium, indium, tin, titanium, zirconium, hafnium, zinc, chromium, manganese, lithium, beryllium, magnesium, iron, phosphorus, cobalt, nickel, arsenic, and antimony.

[0135] In some embodiments, the water-soluble compound is at least one of chloride, fluoride, sulfate, nitrate or acetate.

[0136] In some preferred embodiments, the M' source in the aqueous solution of the M' source is selected from water-soluble aluminum compounds, water-soluble titanium compounds, and water-soluble iron compounds.

[0137] In some embodiments, the water-soluble aluminum compound is selected from at least one of aluminum chloride, aluminum sulfate, aluminum nitrate, and aluminum acetate. In some preferred embodiments, the water-soluble titanium compound is selected from at least one of titanium tetrachloride, titanium sulfate, and ammonium hexafluorotitanate. In some preferred embodiments, the water-soluble iron compound is selected from ferric chloride, ferric sulfate, ferric nitrate, etc.

[0138] In some preferred embodiments, the water-soluble compounds of boron, gallium, indium, tin, zirconium, hafnium, zinc, chromium, manganese, lithium, beryllium, magnesium, phosphorus, cobalt, nickel, arsenic, and antimony are all conventionally used in the art, such as nitrates.

[0139] In the context of this invention, a water-soluble compound refers to a compound that can dissolve in water to form a stable aqueous solution. It should be noted that a water-soluble compound is not necessarily required to have significant water solubility in pure water. In fact, it is sufficient for the compound to dissolve in water to form an aqueous solution under the actual conditions of this invention (e.g., acidic or alkaline conditions). For example, titanium sulfate, which dissolves in water under acidic conditions during its preparation, is also a water-soluble compound.

[0140] In some preferred embodiments, the source of M' is selected from aluminum nitrate and / or ammonium hexafluorotitanate.

[0141] In some embodiments, the preparation method of SCM-45 molecular sieve involves post-treatment of the molecular sieve between the second temperature treatment and calcination in step S30, the post-treatment including solid-liquid separation, washing and drying.

[0142] In the post-processing of this invention, molecular sieves can be separated from the mixture using any conventionally known separation method. Examples of such separation methods include filtration or centrifugation of the mixture. Filtration and centrifugation can be performed in any manner conventionally known in the art. Specifically, as filtration, the mixture can be simply filtered by suction. Washing and drying in this invention can be performed in any manner conventionally known in the art. Specifically, as washing, deionized water can be used.

[0143] Examples of drying temperatures include 40-250°C, preferably 60-150°C, and examples of drying times include 1-30 hours, preferably 8-30 hours, and more preferably 10-20 hours. The drying process can be carried out under normal pressure or under reduced pressure.

[0144] The present invention involves calcining the molecular sieve precursor to remove any present moisture, etc. The calcination can be carried out in any manner conventionally known in the art; for example, the calcination temperature is generally 300-800℃, preferably 400-650℃, and the calcination time is generally 1-10 hours, preferably 3-6 hours. Furthermore, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere.

[0145] The SCM-45 molecular sieve preparation method of the present invention has simple synthesis steps, high operability, wide synthesis range, and is easy to promote. The SCM-45 molecular sieve framework preparation method of the present invention allows the SCM-45 molecular sieve framework to include Si and other elements that can be selected within a certain range, and allows for the customization of catalytic active centers as needed.

[0146] Third aspect

[0147] Thirdly, the present invention provides a molecular sieve composition comprising the SCM-45 molecular sieve described in the first aspect of the present invention, and a binder.

[0148] The SCM-45 molecular sieve described in this invention can be used in combination with other materials to obtain molecular sieve compositions. Examples of these other materials include active materials such as synthetic and natural zeolites, and inactive materials (generally referred to as binders) such as clay, kaolin, silica gel, alumina, silicon dioxide, and magnesium oxide. These other materials can be used individually or in combination in any proportion. The amounts of these other materials used can be directly referenced from conventional amounts used in the art and are not particularly limited.

[0149] Fourth aspect

[0150] Fourthly, the present invention provides the use of the SCM-45 molecular sieve described in the first aspect or the molecular sieve composition described in the third aspect of the present invention in catalytic reactions, adsorption or ion exchange.

[0151] The SCM-45 molecular sieve or a molecular sieve composition containing the SCM-45 molecular sieve described in this invention 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. Accordingly, the at least one component can be partially or substantially completely separated from the mixture of various components, specifically by contacting the mixture with the SCM-45 molecular sieve or a molecular sieve composition containing the SCM-45 molecular sieve to selectively adsorb the component. Furthermore, the SCM-45 molecular sieve or a molecular sieve composition containing the SCM-45 molecular sieve described in this invention can also be used as a catalyst, particularly in organic compound conversion reactions.

[0152] Example

[0153] 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 of 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.

[0154] In this paper, the structure of the molecular sieve was determined by X-ray diffraction (XRD), which was measured using an X-ray powder diffractometer with a Cu-Kα ray source and a Kα1 wavelength. Nickel filter.

[0155] In this invention, an X'Pert PRO X-ray powder diffractometer from Panaco GmbH (Netherlands) was used, with an operating voltage of 40 kV, a current of 40 mA, and a scanning range of 5–40 nm. o .

[0156] In this invention, the scanning electron microscope (SEM) images were obtained using a HITACHI S4800 field emission scanning electron microscope from Japan, under the following test conditions: voltage 3kV, current 50mA.

[0157] In this invention, the silicon and germanium content of the molecular sieve was obtained by ICP testing. The instrument used was an Agilent 725-ES ICP-AES. The molar ratio of the elements was determined by dissolving the sample in hydrofluoric acid.

[0158] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, unless being based on weight would not be in accordance with the common understanding of those skilled in the art.

[0159] Unless otherwise specified, all reagents used in the following embodiments of the present invention are commercially available.

[0160] Unless otherwise specified, "Si / Ge" in this invention refers to the molar ratio of SiO2 to GeO2.

[0161] Example 1

[0162] Dissolve 0.698 g of germanium source (germanium oxide) and 0.408 g of M source (aluminum isopropoxide) in 15.82 g of 1,1,3,5-tetramethylpiperidine hydroxide (1,1,3,5-TMPOH) aqueous solution (20 wt%). Slowly add 6.934 g of silicon source (tetraethyl orthosilicate (TEOS)). Stir at room temperature until hydrolysis is complete. Then, leave the container open and stir overnight to evaporate ethanol, isopropanol, and some water. Add 1 g of hydrofluoric acid (40 wt%), stir until homogeneous, and adjust the water volume until the reaction mixture reaches the following molar composition:

[0163] 0.5(1,1,3,5-TMPOH):0.833SiO2:0.167GeO2:0.025Al2O3:0.5HF:16H2O

[0164] The above mixture was placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in an oven at 175°C for 336 hours. After the reaction, the solid was filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain the precursor SCM-45P. The XRD pattern is shown in Figure 3.

[0165] 0.3 g of precursor SCM-45P was added to 30 g of 12 M HCl solution. The mixture was stirred at 25 °C for 10 minutes for the first temperature treatment, and then placed in a 75 °C water bath for another 120 minutes for the second temperature treatment. After the reaction, the solid was filtered, washed with distilled water, dried at 100 °C, and calcined in a muffle furnace at 550 °C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is shown in Figure 4, and the spectral data are shown in Table 1. The SEM image is shown in Figure 5. Figure 5 shows that the SCM-45 molecular sieve is a plate-like crystal with a plate thickness of approximately 40 nm. The nitrogen adsorption-desorption isotherm is shown in Figure 6. Figure 6 shows that the SCM-45 molecular sieve exhibits a type I isotherm and a specific surface area of ​​457 m². 2 / g, micropore volume is 0.17cm³ 3 / g.

[0166] Table 1

[0167] Example 2

[0168] Dissolve 0.492 g of germanium oxide and 0.272 g of aluminum isopropoxide in 15.82 g of an aqueous solution of 1,1,3,5-tetramethylpiperidine hydroxide (1,1,3,5-TMPOH) (20 wt%). Slowly add 7.342 g of tetraethyl orthosilicate (TEOS). Stir at room temperature until hydrolysis is complete. Then, leave the container open and stir overnight to evaporate ethanol, isopropanol, and some water. Add 1 g of hydrofluoric acid (40 wt%), stir until homogeneous, and adjust the water volume until the reaction mixture reaches the following molar composition:

[0169] 0.5(1,1,3,5-TMPOH):0.882SiO2:0.118GeO2:0.0167Al2O3:0.5HF:12.5H2O

[0170] The above mixture was placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in an oven at 175°C for 336 hours. The solid after reaction was filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain the precursor SCM-45P.

[0171] 0.3 g of precursor SCM-45P was added to 30 g of 12 M HCl solution. The mixture was stirred at 25 °C for 10 minutes for the first temperature treatment, and then placed in a 45 °C water bath for another 5 hours for the second temperature treatment. After the reaction, the solid was filtered, washed with distilled water, dried at 100 °C, and calcined in a muffle furnace at 550 °C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is shown in Figure 7, and the spectral data are shown in Table 2. The SEM image is shown in Figure 8. Figure 8 shows that the SCM-45 molecular sieve is a plate-like crystal with a plate thickness of approximately 35 nm. The nitrogen adsorption-desorption isotherm is shown in Figure 9. Figure 9 shows that the SCM-45 molecular sieve exhibits a type I isotherm and a specific surface area of ​​420 m². 2 / g, micropore volume is 0.15cm³ 3 / g.

[0172] Table 2

[0173] Example 3

[0174] Dissolve 0.832 g of germanium oxide and 0.326 g of aluminum isopropoxide in 15.82 g of an aqueous solution of 1,1,3,5-tetramethylpiperidine hydroxide (1,1,3,5-TMPOH) (20 wt%). Slowly add 7.342 g of tetraethyl orthosilicate (TEOS). Stir at room temperature until hydrolysis is complete. Then, leave the container open and stir overnight to evaporate ethanol, isopropanol, and some water. Add 1 g of hydrofluoric acid (40 wt%), stir until homogeneous, and adjust the water volume until the reaction mixture reaches the following molar composition:

[0175] 0.5(1,1,3,5-TMPOH):0.8SiO2:0.2GeO2:0.02Al2O3:0.5HF:17.5H2O

[0176] The above mixture was placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in an oven at 175°C for 336 hours. The solid after reaction was filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain the precursor SCM-45P.

[0177] 0.3 g of precursor SCM-45P was placed on a porous polytetrafluoroethylene (PTFE) membrane and then placed inside a PTFE liner. 60 g of 12M HCl solution was added to the bottom of the reactor to allow the HCl vapor to contact the precursor SCM-45P. The reactor was subjected to a first temperature treatment at 20°C for 2 hours. Then, the PTFE liner was placed in a stainless steel reactor and placed in a 68°C oven for a second temperature treatment, which lasted for 6 hours. After the reaction, the reactor was removed, cooled, and the solid was filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The spectral data are shown in Table 3.

[0178] Table 3

[0179] Example 4

[0180] Take 0.3g of the precursor SCM-45P from Example 3, add 30g of 8M HCl solution, and stir at 27°C for 10 minutes for the first temperature treatment. Then, place it in a 50°C water bath and continue stirring for 7 hours for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is similar to that of Example 3.

[0181] Example 5

[0182] Take 0.3g of the precursor SCM-45P from Example 3, add 45g of 6M HCl solution, and stir at 18°C ​​for 15 minutes for the first temperature treatment. Then, place it in an 80°C water bath and continue stirring for 3 hours for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is similar to that of Example 3.

[0183] Example 6

[0184] Dissolve 1.2 g of germanium oxide and 0.544 g of aluminum isopropoxide in 15.82 g of an aqueous solution of 1,1,3,5-tetramethylpiperidine hydroxide (1,1,3,5-TMPOH) (20 wt%). Slowly add 5.942 g of tetraethyl orthosilicate (TEOS). Stir at room temperature until hydrolysis is complete. Then, leave the container open and stir overnight to evaporate ethanol, isopropanol, and some water. Add 1 g of hydrofluoric acid (40 wt%), stir until homogeneous, and adjust the water volume until the reaction mixture reaches the following molar composition:

[0185] 0.5(1,1,3,5-TMPOH):0.714SiO2:0.286GeO2:0.033Al2O3:0.5HF:20H2O

[0186] The above mixture was placed in a crystallization vessel lined with polytetrafluoroethylene and crystallized in an oven at 175°C for 336 hours. The solid after reaction was filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain the precursor SCM-45P.

[0187] 0.3 g of precursor SCM-45P was added to 30 g of 12 M HCl solution. The mixture was stirred at 15 °C for 15 minutes for the first temperature treatment, and then placed in a 95 °C water bath for another 8 hours for the second temperature treatment. After the reaction was completed, the solid was filtered, washed with distilled water, dried at 100 °C, and calcined in a muffle furnace at 550 °C for 5 hours to obtain SCM-45 molecular sieve. The spectral data are shown in Table 4.

[0188] Table 4

[0189] Example 7

[0190] Take 0.3g of the precursor SCM-45P from Example 6, add 36g of 9M HCl solution, and stir at 22°C for 10 minutes for the first temperature treatment. Then, place it in a 52°C water bath and continue stirring for 15 hours for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is similar to that of Example 6.

[0191] Example 8

[0192] Take 0.3g of the precursor SCM-45P from Example 6, add 54g of 10M HNO3 solution, and stir at 25°C for 10 minutes for the first temperature treatment. Then, place it in a 65°C water bath and continue stirring for 10 hours for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is similar to that of Example 6.

[0193] Example 9

[0194] Take 0.3g of the precursor SCM-45P from Example 1, add 15g of 3M Al(NO3)3 solution, and stir at 18℃ for 10 minutes for the first temperature treatment. Then, place it in a 90℃ water bath and continue stirring for 90 minutes for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100℃, and calcined in a muffle furnace at 550℃ for 5 hours to obtain a high-silicon aluminum-containing SCM-45 molecular sieve with Si / Al = 115. The XRD pattern data are shown in Table 5.

[0195] Table 5

[0196] Example 10

[0197] Take 0.3g of the precursor SCM-45P from Example 1, add 15g of 1M (NH4)2TiF6 solution and 15g of 5M HCl solution, and stir at 20°C for 10 minutes for the first temperature treatment. Then, place it in a 60°C water bath and continue stirring for 4 hours for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain a high-silicon titanium-containing SCM-45 molecular sieve with Si / Ti = 105. The XRD pattern is similar to that in Figure 4.

[0198] Example 11

[0199] Take 0.3g of the precursor SCM-45P from Example 6, add 48g of 10M HCl solution, and stir at 24°C for 12 minutes for the first temperature treatment. Then, place it in a 90°C water bath and continue stirring for 30 minutes for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is similar to that of Example 6.

[0200] Example 12

[0201] Take 0.3g of the precursor SCM-45P from Example 3, add 24g of 10M HCl solution, and stir at 20°C for 20 minutes for the first temperature treatment. Then, place it in an 80°C water bath and continue stirring for 9 hours for the second temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100°C, and calcined in a muffle furnace at 550°C for 5 hours to obtain SCM-45 molecular sieve. The XRD pattern is similar to that of Example 3.

[0202] Comparative Example 1

[0203] Take 0.3g of the precursor SCM-45P from Example 1, add 30g of 12M HCl solution, and stir at 25℃ for 10 minutes for the first temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100℃, and calcined in a muffle furnace at 550℃ for 5 hours to obtain the final molecular sieve product. The XRD pattern is shown in Figure 10, and the spectral data is shown in Table 6. It can be found that the pattern is significantly different from that of SCM-45 molecular sieve.

[0204] Table 6

[0205] Comparative Example 2

[0206] Take 0.3g of the precursor SCM-45P from Example 1, add 30g of 12M HCl solution, and stir at 25℃ for 8h for the first temperature treatment. After the reaction is complete, the solid is filtered, washed with distilled water, dried at 100℃, and calcined in a muffle furnace at 550℃ for 5 hours to obtain the final molecular sieve product. The XRD diffraction pattern is the same as that of Comparative Example 1.

[0207] The parameters in the above embodiments are shown in Table 7.

[0208] Table 7

[0209] In Table 7, the Si / Ge ratio of the molecular sieve precursor feed refers to the molar ratio of SiO2 and GeO2 in the silicon source and germanium source; the Si / Ge ratio of the molecular sieve precursor product refers to the molar ratio of SiO2 and GeO2 in the molecular sieve precursor SCM-45P; and the Si / Ge ratio of the molecular sieve refers to the molar ratio of SiO2 and GeO2 in the SCM-45 molecular sieve prepared in Examples 1-10.

[0210] As shown in Table 7, due to the degermanium removal process of the molecular sieve precursor after treatment with the treatment solution, the final silicon-germanium ratio (molar ratio of SiO2 and GeO2) in the SCM-45 molecular sieve is ≥40. At this point, the germanium content in the SCM-45 molecular sieve is significantly lower than that in the molecular sieve precursor.

[0211] 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-45 molecular sieve, the X-ray diffraction pattern of which includes diffraction peaks at 2θ of 7.13°±0.30°, 8.10°±0.30°, 13.00°±0.30°, and 19.41°±0.30°; Preferably, the diffraction peak with 2θ of 7.13°±0.30° is the strongest peak.

2. The SCM-45 molecular sieve of claim 1, wherein, The X-ray diffraction pattern of the SCM-45 molecular sieve also includes a diffraction peak with a 2θ of 26.17° ± 0.30°.

3. The SCM-45 molecular sieve of claim 1 or 2, wherein, The X-ray diffraction pattern of the SCM-45 molecular sieve also includes one or more diffraction peaks with 2θ values ​​of 22.00°±0.30° and 27.22°±0.30°.

4. The SCM-45 molecular sieve of any one of claims 1-3, wherein, The X-ray diffraction pattern of the SCM-45 molecular sieve also includes one or more diffraction peaks with 2θ values ​​of 14.82°±0.30°, 16.03°±0.30°, 20.18°±0.30°, and 22.70°±0.30°.

5. The SCM-45 molecular sieve of any one of claims 1-4, wherein, The X-ray diffraction pattern of the SCM-45 molecular sieve includes the relative intensity characteristics of the diffraction peaks shown in Table A: Table A Preferably, the X-ray diffraction pattern further includes the relative intensity characteristics of the diffraction peaks as shown in any one or more rows of Table B: Table B Preferably, the X-ray diffraction pattern of the SCM-45 molecular sieve includes the relative intensity characteristics of the diffraction peaks shown in Table C: Table C Preferably, the X-ray diffraction pattern of the SCM-45 molecular sieve further includes the relative intensity characteristics of the diffraction peaks shown in any one or more rows of Table D: Table D 6. The SCM-45 molecular sieve of any one of claims 1-5, wherein, The SCM-45 molecular sieve has at least one of the following characteristics: In the SCM-45 molecular sieve, the molar ratio of SiO2 to GeO2 is ≥40, preferably ≥45; Preferably, the SCM-45 molecular sieve further comprises MO m / 2 wherein M is a framework element other than silicon and germanium, m is the valence of the M element, m = 1-7, and the molar ratio of SiO2to MO m / 2 is > 20, preferably 50-200 (inclusive). Preferably, the SCM-45 molecular sieve has a chemical composition of x SiO2·y GeO2·z MO m / 2 or x SiO2·y GeO2, wherein x / y > 40, preferably x / y > 45, and in the presence of z, x / z > 20, preferably 200 > x / z > 50; Preferably, the framework element M of the SCM-45 molecular sieve, excluding silicon and germanium, is selected from at least one of Group IIIA, Group IVA, Group IVB, Group IIB, Group VIB, Group VIIB, Group IA, Group IIA, Group VIII, Group VA, or Group VB elements, and is more preferably selected from at least one of aluminum, boron, gallium, indium, tin, titanium, zirconium, hafnium, zinc, chromium, manganese, lithium, beryllium, magnesium, iron, phosphorus, vanadium, cobalt, nickel, arsenic, or antimony. The SCM-45 molecular sieve has a plate-like crystal morphology. Preferably, the thickness of the SCM-45 molecular sieve sheets is 20–500 nm; The specific surface area of the SCM-45 molecular sieve is greater than 350 m 2 / g, The SCM-45 molecular sieve has a micropore volume greater than 0.14 cm3 / g 3 / g, The SCM-45 molecular sieve includes a layered structure and interlayer connecting units, wherein the interlayer connecting units include single four-membered rings and double four-membered rings; preferably, the molar ratio of the single four-membered rings to the double four-membered rings is 1:2-2:1, more preferably about 1:

1.

7. A method for preparing SCM-45 molecular sieve according to any one of claims 1-6, comprising the following steps: S10, a mixture of silicon source, germanium source, fluorine source, structure directing agent, water and optional additional framework element M source, are used to obtain a mixture; S20. The mixture is subjected to a crystallization reaction to obtain a molecular sieve precursor; S30. The molecular sieve precursor is brought into contact with the treatment liquid and subjected to treatment at a first temperature and a second temperature in sequence, and then calcined to obtain SCM-45 molecular sieve. The treatment solution is selected from at least one of an acid solution, an alkaline solution, or an aqueous solution of an additional framework element M' source. The first temperature is 5℃-40℃; the second temperature is 41℃-100℃.

8. The preparation method according to claim 7, characterized in that, In step S10, at least one of the following characteristics is satisfied: 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 tetraalkoxysilane; The germanium source is selected from at least one of germanium oxide, germanium nitrate, and tetraalkoxy germanium; The M source is selected from at least one of the following group elements other than silicon and germanium: group IIIA, group IVA, group IVB, group IIB, group VIB, group VIIB, group IA, group IIA, group VIII, group VA, or group VB elements, as well as their elements, chlorides, oxides, hydroxides, nitrates, sulfates, carbonates, acetates, isopropoxides, or metaacids. Preferably, the M source is selected from at least one of the following: elemental aluminum, chloride, oxide, hydroxide, nitrate, sulfate, carbonate, acetate, isopropoxide, or metaacid salt; Preferably, the M source is selected from at least one of aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum chloride, boehmite, alumina, aluminum hydroxide, silica-alumina zeolite molecular sieve, aluminum carbonate, elemental aluminum, aluminum isopropoxide, and aluminum acetate. The fluorine source is selected from at least one of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride; The structure directing agent is selected from those containing 1,1,3,5-tetraalkylpiperidine onium ions; preferably, the structure directing agent is 1,1,3,5-tetramethylpiperidine hydroxide.

9. The production method according to claim 7 or 8, characterized by, In step S10, at least one of the following characteristics is satisfied: The silicon source is calculated as SiO2, the germanium source as GeO2, the M source as oxide MO m / 2 wherein m is the valence of the M element and m = 1 to 7, the fluorine source as F, In the mixture, the molar ratio of SiO2 to GeO2 is (2-10):1; the sum of the number of moles of SiO2and GeO2to the number of moles of MO m / 2 is in the range of (15-30): 1; In the mixture, the molar ratio of the sum of the moles of SiO2 and GeO2 to F is 1:(0.1-1); In the mixture, the sum of the molar numbers of SiO2 and GeO2 is in a molar ratio of 1:(0.1-1) to the structure directing agent. In the mixture, the sum of the molar numbers of SiO2 and GeO2 and the molar ratio of water are 1:(12.5-25); Preferably, the molar ratio of structure directing agent, SiO2, GeO2, MO m / 2 F and water in the mixture is 0.5 : (0.667-0.909) : (0.091-0.333) : (0.0333-0.0667) : 0.5 : (12.5-25).

10. The production method according to any one of claims 7 to 9, characterized by, In step S20, at least one of the following characteristics is satisfied: The temperature of the crystallization reaction is 100-200℃, preferably 110-190℃, and more preferably 155-175℃; The crystallization reaction takes 72-600 hours, preferably 96-480 hours, and more preferably 120-360 hours.

11. The production method according to any one of claims 7 to 10, characterized by, Step S25 is also included between steps S20 and S30: The molecular sieve precursor undergoes post-processing, which includes solid-liquid separation, washing, drying, and calcination. Preferably, the solid-liquid separation is performed by filtration; Preferably, the washing process involves washing with water once or multiple times; Preferably, the drying is carried out at 40-250°C for 1-30 hours; Preferably, the calcination temperature is 300℃-800℃, more preferably 400℃-650℃; Preferably, the roasting time is 1h-10h, and more preferably 3h-6h.

12. The production method according to any one of claims 7 to 11, characterized by, In step S30, when the Si / Ge ratio in the molecular sieve precursor is 4 < Si / Ge ≤ 5.5, and the second temperature is 41℃-55℃, the second temperature treatment time is ≥ 10.5h; and / or When the Si / Ge ratio in the molecular sieve precursor is 4 < Si / Ge ≤ 5.5, and the second temperature is 56℃-70℃, the treatment time at the second temperature is ≥ 8.5h; and / or When the Si / Ge ratio in the molecular sieve precursor is 4 < Si / Ge ≤ 5.5, and the second temperature is 71℃-85℃, the treatment time at the second temperature is ≥ 6.5h; and / or When the ratio of 4 to Si / Ge in the molecular sieve precursor is ≤5.5, and the second temperature is 86℃-100℃, the treatment time at the second temperature is ≥4.5h. When the molecular sieve precursor has a Si / Ge ratio of 5.5 < 7 and the second temperature is 41℃-55℃, the second temperature treatment time is 5-9 hours; and / or When the Si / Ge ratio in the molecular sieve precursor is 5.5 < Si / Ge ≤ 7, and the second temperature is 56℃-70℃, the second temperature treatment time is 80 min-7 h; and / or When the Si / Ge ratio in the molecular sieve precursor is 5.5 < Si / Ge ≤ 7, and the second temperature is 71℃-85℃, the second temperature treatment time is 60 min-5 h; and / or When the Si / Ge ratio in the molecular sieve precursor is 5.5 < Si / Ge ≤ 7, and the second temperature is 86℃-100℃, the second temperature treatment time is 30 min-3 h; and / or When the Si / Ge ratio in the molecular sieve precursor is greater than 7, and the second temperature is 41℃-55℃, the treatment time at the second temperature is 3.5-7 hours; and / or When the Si / Ge ratio in the molecular sieve precursor is greater than 7, and the second temperature is 56℃-70℃, the treatment time at the second temperature is 1.5-5 hours; and / or When the Si / Ge ratio in the molecular sieve precursor is greater than 7, and the second temperature is 71℃-85℃, the treatment time at the second temperature is 1-3.5 h; and / or When the Si / Ge ratio in the molecular sieve precursor is greater than 7, and the second temperature is 86℃-100℃, the treatment time at the second temperature is 0.5-3h.

13. The production method according to any one of claims 7 to 12, characterized by, In step S30, at least one of the following characteristics is satisfied: The mass ratio of the treatment liquid to the molecular sieve precursor is 20-300; preferably 50-200. The acid solution is selected from at least one of HCl aqueous solution, HCl alcoholic solution, H2SO4 aqueous solution, HNO3 aqueous solution, and acetic acid solution, preferably HCl aqueous solution; Preferably, the concentration of the acid solution is 0.01-20M, more preferably 0.01-14M; The alkaline solution is selected from an ammonia solution; The concentration of the alkaline solution is 0.1-30 wt%, preferably 0.5-25 wt%. The M' source in the aqueous solution is selected from at least one water-soluble compound of a group IIIA, group IVA, group IVB, group IIB, group VIB, group VIIB, group IA, group IIA, group VIII, group VA, or group VB element; preferably selected from at least one water-soluble compound of aluminum, boron, gallium, indium, tin, titanium, zirconium, hafnium, zinc, chromium, manganese, lithium, beryllium, magnesium, iron, phosphorus, cobalt, nickel, arsenic, or antimony; preferably, the water-soluble compound is at least one of chloride, fluoride, sulfate, nitrate, or acetate. Preferably, the source M' is selected from water-soluble aluminum compounds, water-soluble titanium compounds, and water-soluble iron compounds; Preferably, the water-soluble aluminum compound is selected from at least one of aluminum chloride, aluminum sulfate, aluminum nitrate, and aluminum acetate; The water-soluble titanium compound is selected from at least one of titanium tetrachloride, titanium sulfate, and ammonium hexafluorotitanate; The water-soluble iron compound is selected from at least one of ferric chloride, ferric sulfate, and ferric nitrate; More preferably, the source of M' is selected from aluminum nitrate and / or ammonium hexafluorotitanate.

14. The production method according to any one of claims 7 to 13, characterized by, In step S30, the molecular sieve is post-treated between the second temperature treatment and calcination. The post-treatment includes solid-liquid separation, washing, and drying. Preferably, the solid-liquid separation is performed by filtration; Preferably, the washing process involves washing with water once or multiple times; Preferably, the drying is carried out at 40-250°C for 1-30 hours; Preferably, the calcination temperature is 300℃-800℃, more preferably 400℃-650℃; The roasting time is 1h-10h, preferably 3h-6h.

15. A molecular sieve composition comprising the SCM-45 molecular sieve according to any one of claims 1-6, and a binder; Preferably, the binder is selected from at least one of clay, kaolin, silica gel, alumina, silicon dioxide, and magnesium oxide.

16. The use of the SCM-45 molecular sieve according to any one of claims 1-6 or the molecular sieve composition according to claim 15 in catalytic reactions, adsorption or ion exchange.

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