SCM-25 molecular sieve based on silicon and germanium, its production method and use

Abstract

The present invention relates to a silicon- and germanium-based molecular sieve, a method for preparing the molecular sieve, and its use. The molecular sieve of the present invention has a framework chemical composition represented by the formula "SiO2·1 / nGeO2", with a silicon / germanium molar ratio of 0.1≦n≦30. The molecular sieve of the present invention has a unique X-ray diffraction pattern and has good application prospects in the adsorptive separation, ion exchange, and catalytic conversion of organic compounds.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to an SCM-25 molecular sieve, a method for its preparation, and its use.

[0002] [Background technology] Zeolite, also known as molecular sieve, is a type of porous crystalline material. There are 245 kinds of molecular sieves with known structures discovered so far, and molecular sieves with new structures are still emerging. Due to their regular molecular size pore structure, strong acidity and high hydrothermal stability, molecular sieves are widely used in the fields of catalysis, adsorption, ion exchange, etc., where they play an irreplaceable role. The framework of a molecular sieve is typically composed of coordinated tetrahedra (TO4) connected by common vertices (typically oxygen atoms). For molecular sieves, the tetrahedra in the framework are mainly SiO4 tetrahedra and AlO4 tetrahedra. These two tetrahedra can be replaced by other tetrahedra to form molecular sieves or molecular sieve analogues with different framework structures. For example, AlO4 tetrahedra can be replaced by GaO4 or ZnO4 tetrahedra. Together with the SiO4 tetrahedra, these form the framework of the heteroatomic molecular sieve. Furthermore, Ge and Si have similar coordination properties and can also form tetrahedral coordination structures, and the connection between GeO4 and SiO4 can form many novel germanium-containing molecular sieves or molecular sieve-like structures.

[0003] In 1959, Barrer et al. were the first to try to introduce Ge element into the synthesis of molecular sieves, and produced aluminum germanate salts with a structure similar to A-type and X-type molecular sieves (J.Chem.Soc.,1959,195-208). About 40 years later, Yaghi was the first to produce a new structure of germanium-containing molecular sieve ASU-7 (J.Am.Chem.Soc.1998,120,10569-10570). The framework structure of this molecular sieve is entirely composed of GeO4 tetrahedra. After that, many researchers began to try to synthesize new structures of germanium-containing molecular sieves. Among them, the research of Professor Colma's research group at the Polytechnic University of Valencia in Spain has attracted the most attention. Some types of silicogermanate molecular sieves that have been extensively studied include UTL (US 7074385), BEC (US 6896869), STW (Nature Mater., 2008, 7, 381-385), etc.

[0004] SUMMARY OF THEINVENTION The present invention provides silicon and germanium based molecular sieves and methods for making said molecular sieves.

[0005] The technical schemes adopted by the present invention are as follows: (Summary 1) A molecular sieve having an X-ray diffraction pattern substantially as shown in the following table,

[0006] [Table 1]

[0007] Preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the table below:

[0008] [Table 2]

[0009] More preferably, the molecular sieve, wherein said X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as set out in the table below.

[0010] [Table 3]

[0011] (Summary 2) A molecular sieve having an X-ray diffraction pattern substantially as shown in the following table,

[0012] [Table 4]

[0013] Preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the table below:

[0014] [Table 5]

[0015] More preferably, the molecular sieve, wherein said X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as set out in the table below.

[0016] [Table 6]

[0017] (Summary 3) A molecular sieve having an X-ray diffraction pattern substantially as shown in the following table,

[0018] [Table 7]

[0019] Preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the table below:

[0020] [Table 8]

[0021] More preferably, the molecular sieve, wherein said X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as set out in the table below.

[0022] [Table 9]

[0023] (Summary 4) A molecular sieve having an X-ray diffraction pattern substantially as shown in the table below,

[0024] [Table 10]

[0025] Preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the table below:

[0026] [Table 11]

[0027] More preferably, the molecular sieve, wherein said X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as set out in the table below.

[0028] [Table 12]

[0029] (Summary 5) A molecular sieve having an X-ray diffraction pattern substantially as shown in the table below,

[0030] [Table 13]

[0031] Preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the table below:

[0032] [Table 14]

[0033] More preferably, the molecular sieve, wherein said X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as set out in the table below.

[0034] [Table 15]

[0035] (Summary 6) A molecular sieve having an X-ray diffraction pattern substantially as shown in the following table,

[0036] [Table 16]

[0037] Preferably, the X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the table below:

[0038] [Table 17]

[0039] More preferably, the molecular sieve, wherein said X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as set out in the table below.

[0040] [Table 18]

[0041] (Summary 7) The molecular sieve according to any one of the above technical solutions, wherein the molecular sieve is based on silicon and germanium.

[0042] (Summary 8) A molecular sieve described in any one of the technical solutions, wherein the molecular sieve has no hysteresis loop in the N2 adsorption-desorption isotherm at 77K.

[0043] (Summary 9) The molecular sieve according to any one of the technical solutions, wherein the calcined form of the molecular sieve has a framework chemical composition represented by the formula "SiO2·1 / nGeO2", and the silicon / germanium molar ratio is 0.1≦n≦30, preferably 0.25≦n≦20, more preferably 0.5≦n≦15, and even more preferably 1≦n≦5.

[0044] (Summary 10) The molecular sieve in the synthesis state has a framework chemical composition represented by the formula "kF mQ SiO2 1 / nGeO2 pH2O", the silicon / germanium molar ratio is 0.1≦n≦30, preferably 0.25≦n≦20, more preferably 0.5≦n≦15, and even more preferably 1≦n≦5; 0.05≦k≦1.0, preferably 0.05≦k≦0.5, more preferably 0.1≦k≦0.5, and even more preferably 0.1≦k≦0.4; Q is an organic template agent, 0.01≦m≦1.0, preferably 0.02≦m≦0.5, more preferably 0.05≦m≦0.5, and even more preferably 0.05≦m≦0.3; The organic templating agent is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions or represented by the following structural formula, preferably 1,1,3,5-tetramethylpiperidinium hydroxide;

[0045] [ka]

[0046] In the above formula, R1-R4 are each independently H or C 1-4 Alkyl, preferably C 1-2 is alkyl, more preferably -CH3; - is a halide ion (e.g., Cl - , Br - and I - ) and hydroxide ion (OH - ), preferably hydroxide ion (OH - ) and; The molecular sieve according to any one of the above technical solutions, wherein 0.005≦p≦0.5, preferably 0.01≦p≦0.4, more preferably 0.01≦p≦0.3, and even more preferably 0.02≦p≦0.2.

[0047] (Summary 11) A molecular sieve according to any one of the above technical solutions, wherein 10% or less of the Ge atoms in the molecular sieve are replaced by atoms of at least one element other than silicon and germanium.

[0048] (Summary 12) The element other than silicon and germanium is at least one selected from the group consisting of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium, and indium; Preferably, the molecular sieve according to any one of the above technical solutions is at least one selected from the group consisting of aluminum and titanium.

[0049] (Summary 13) A method for producing a molecular sieve by crystallizing a mixture comprising a silicon source, a germanium source, a fluorine source, an organic templating agent Q, and water, or a mixture formed from a silicon source, a germanium source, a fluorine source, an organic templating agent Q, and water; and optionally, calcining the resulting molecular sieve; The organic templating agent Q is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions, or is represented by the following structural formula, preferably 1,1,3,5-tetramethylpiperidinium hydroxide:

[0050] [ka]

[0051] R1-R4 are each independently H or C 1-4 alkyl, preferably C 1-2 is alkyl, more preferably -CH3; - is a halide ion (e.g., Cl - , Br - and I - ) and hydroxide ion (OH - ), preferably hydroxide ion (OH - ) a method for producing a molecular sieve based on silicon and germanium.

[0052] (Summary 14) The silicon source is at least one selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, and tetraethyl orthosilicate; The method for producing a molecular sieve according to any one of the above technical solutions, wherein the germanium source is at least one selected from the group consisting of germanium oxide, germanium nitrate, and germanium tetraalkoxide (alkoxide refers to C1-C6 alkoxide).

[0053] In the above technical solution, the molar ratio of the organic templating agent Q, the silicon source (as SiO2), the germanium source (as GeO2), the fluorine source (as F) and water is Q:SiO2:GeO2:F:H2O=0.15-4:1:0.033-10:0.2-4:0.5-50, preferably Q:SiO2:GeO2:F:H2O =0.25-3.5:1:0.05-4:0.35-3.5:1-35, more preferably Q:SiO2:GeO2:F:H2O=0.3-2.5:1:0.067-2:0.4-2.5:1.5-25, and even more preferably Q:SiO2:GeO2:F:H2O=0.35-1.5:1:0.2-1:0.45-2:2-15.

[0054] (Summary 15) The method for producing a molecular sieve according to any one of the above technical solutions, wherein the fluorine source comprises at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, preferably at least one selected from the group consisting of hydrofluoric acid and ammonium fluoride.

[0055] (Summary 16) The method for producing a molecular sieve according to any one of the technical solutions, wherein the crystallization conditions include crystallization at 100°C to 200°C for 30 hours to 400 hours; preferably crystallization at 110°C to 190°C for 48 hours to 360 hours; more preferably crystallization at 120°C to 180°C for 72 hours to 320 hours.

[0056] (Summary 17) The mixture further comprises a source containing elements other than silicon and germanium; Preferably, the source comprises at least one selected from the group consisting 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; More preferably, it comprises at least one oxide source selected from the group consisting of a boron oxide source, an alumina source, a gallium oxide source, a titania source, a zirconia source, a hafnia source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source; The method for producing a molecular sieve according to any one of the above technical solutions, wherein the molar ratio of the oxide source (as the corresponding oxide) to the germanium source (as GeO2) is (0.01-0.1):1, preferably (0.015-0.08):1.

[0057] (Summary 18) A molecular sieve composition comprising a molecular sieve according to any one of the technical solutions or a molecular sieve produced by the method for producing a molecular sieve according to any one of the technical solutions, and a binder.

[0058] (Summary 19) Use of a molecular sieve according to any one of the preceding technical solutions, a molecular sieve produced by the method for producing a molecular sieve according to any one of the preceding technical solutions, or a molecular sieve composition according to any one of the preceding technical solutions as an adsorbent or catalyst.

[0059] In accordance with the present invention, the silicon and germanium based molecular sieves involved have a framework structure not previously available in the art.

[0060] According to the present invention, the silicon and germanium based molecular sieves involved have a channel structure with regular molecular dimensions, relatively strong acidity, ion exchange capacity, and high thermal stability.

[0061] According to the present invention, the method for preparing molecular sieves based on silicon and germanium involves simple synthesis steps, has strong operability and wide synthesis field, and is convenient for popularization.

[0062] In one aspect of the present invention, the present invention also provides the following embodiments.

[0063] (Embodiment 1) Molecular sieve SCM-25, wherein the SCM-25 molecular sieve has an X-ray diffraction pattern substantially as shown in the table below.

[0064] [Table 19]

[0065] (Embodiment 2) The X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as set forth in the table below:

[0066] [Table 20]

[0067] 2. The molecular sieve SCM-25 according to embodiment 1, wherein said X-ray crystallographic pattern optionally further comprises X-ray diffraction peaks substantially as shown in the table below.

[0068] [Table 21]

[0069] (Embodiment 3) The calcined form of the molecular sieve has a framework chemical composition represented by the formula "SiO2·1 / nGeO2", The molecular sieve SCM-25 according to embodiment 1, wherein the silicon / germanium molar ratio is 0.1≦n≦30, preferably 0.25≦n≦20, more preferably 0.5≦n≦15, and even more preferably 1≦n≦5.

[0070] (Embodiment 4) The molecular sieve in the as-synthesized form has a framework chemical composition represented by the formula "kF mQ SiO2 1 / nGeO2 pH2O", the silicon / germanium molar ratio is 0.1≦n≦30, preferably 0.25≦n≦20, more preferably 0.5≦n≦15, and even more preferably 1≦n≦5; 0.05≦k≦1.0, preferably 0.05≦k≦0.5, more preferably 0.1≦k≦0.5, and even more preferably 0.1≦k≦0.4; Q is an organic templating agent, 0.01≦m≦1.0, preferably 0.02≦m≦0.5, more preferably 0.05≦m≦0.5, and even more preferably 0.05≦m≦0.3; The organic templating agent is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions or represented by the following structural formula, preferably 1,1,3,5-tetramethylpiperidinium hydroxide;

[0071] [ka]

[0072] In the above formula, R1-R4 are each independently H or C 1-4 Alkyl, preferably C 1-2 is alkyl, more preferably -CH3; - is a halide ion (e.g., Cl - , Br - and I - ) and hydroxide ion (OH - ), preferably hydroxide ion (OH - ) and; The molecular sieve SCM-25 according to embodiment 1, characterized in that 0.005≦p≦0.5, preferably 0.01≦p≦0.4, more preferably 0.01≦p≦0.3, and even more preferably 0.02≦p≦0.2.

[0073] (Embodiment 5) The molecular sieve SCM-25 of embodiment 1, characterized in that 10% or less of the Ge atoms in the molecular sieve are replaced by atoms of at least one element other than silicon and germanium.

[0074] (Embodiment 6) The element other than silicon and germanium is at least one selected from the group consisting of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium; Preferably, the molecular sieve SCM-25 according to embodiment 5 is characterized in that it is at least one selected from the group consisting of aluminum and titanium.

[0075] (Embodiment 7) A method for producing a molecular sieve comprising crystallizing a mixture comprising a silicon source, a germanium source, a fluorine source, an organic templating agent Q and water, or a mixture formed from a silicon source, a germanium source, a fluorine source, an organic templating agent Q and water; and optionally, calcining the resulting molecular sieve; The organic templating agent Q is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions, or is represented by the following structural formula, preferably 1,1,3,5-tetramethylpiperidinium hydroxide:

[0076] [ka]

[0077] R1-R4 are each independently H or C 1-4 alkyl, preferably C 1-2 is alkyl, more preferably -CH3; - is a halide ion (e.g., Cl - , Br - and I - ) and hydroxide ion (OH - ), preferably hydroxide ion (OH - ) A method for producing SCM-25 molecular sieve.

[0078] (Embodiment 8) The silicon source is at least one selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite molecular sieve, and tetraethyl orthosilicate; The germanium source is at least one selected from the group consisting of germanium oxide, germanium nitrate, and germanium tetraalkoxide; The molar ratio of the organic templating agent Q, the silicon source (as SiO2), the germanium source (as GeO2), the fluorine source (as F) and water is Q:SiO2:GeO2:F:H2O=0.15-4:1:0.033-10:0.2-4:0.5-50, preferably Q:SiO2:GeO2:F:H2O=0.25-3.5:1:0.05-4:0.35-3. The method for producing molecular sieve SCM-25 according to embodiment 7, characterized in that Q:SiO2:GeO2:F:H2O=0.5:1-35, more preferably Q:SiO2:GeO2:F:H2O=0.3-2.5:1:0.067-2:0.4-2.5:1.5-25, and even more preferably Q:SiO2:GeO2:F:H2O=0.35-1.5:1:0.2-1:0.45-2:2-15.

[0079] (Embodiment 9) The method for producing molecular sieve SCM-25 according to embodiment 7, characterized in that the fluorine source comprises at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, preferably at least one selected from the group consisting of hydrofluoric acid and ammonium fluoride.

[0080] (Embodiment 10) A method for producing molecular sieve SCM-25 according to embodiment 7, characterized in that the crystallization conditions include crystallization at 100°C to 200°C for 30 to 400 hours; preferably crystallization at 110°C to 190°C for 48 to 360 hours; and more preferably crystallization at 120°C to 180°C for 72 to 320 hours.

[0081] (Embodiment 11) The mixture further comprises a source containing elements other than silicon and germanium; Preferably, the source comprises at least one selected from the group consisting 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; More preferably, it comprises at least one oxide source selected from the group consisting of a boron oxide source, an alumina source, a gallium oxide source, a titania source, a zirconia source, a hafnia source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source; The method for producing molecular sieve SCM-25 according to embodiment 7, characterized in that the molar ratio of the oxide source (as the corresponding oxide) to the germanium source (as GeO2) is (0.01-0.1):1, preferably (0.015-0.08):1.

[0082] (Embodiment 12) A molecular sieve composition comprising the molecular sieve SCM-25 described in any one of embodiments 1 to 6, or the molecular sieve SCM-25 produced by the method for producing the molecular sieve SCM-25 described in any one of embodiments 7 to 11, and a binder.

[0083] (Embodiment 13) Use of the molecular sieve SCM-25 described in any one of embodiments 1 to 6, the molecular sieve SCM-25 produced by the method for producing the molecular sieve SCM-25 described in any one of embodiments 7 to 11, or the molecular sieve composition described in embodiment 12 as an adsorbent or catalyst.

[0084] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an X-ray diffraction (XRD) pattern of the sample obtained in Example 1 before firing; FIG. 2 is an X-ray diffraction (XRD) pattern of the calcined sample obtained in Example 1; FIG. 3 is a scanning electron microscope (SEM) photograph of the sample obtained in Example 1; FIG. 4 is the N2 adsorption-desorption isotherm at 77 K for the sample obtained in Example 1.

[0085] Detailed Description In order to facilitate the understanding of the present invention, the following examples of the present invention are provided.However, those skilled in the art should understand that these examples are only for the purpose of helping to understand the present invention, and should not be considered as specific limitations on the present invention.The end points of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values.

[0086] All publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety.Unless otherwise defined, all technical and scientific terms used herein have the meanings that are commonly understood by those skilled in the art.In the event of discrepancy, the present specification, including definitions, shall prevail.

[0087] In the context of this specification, the silicon and germanium based molecular sieve of the present invention may also be referred to as the molecular sieve of the present invention, or as the SCM-25 molecular sieve, or as the silicon and germanium based SCM-25 molecular sieve.

[0088] In the context of this specification, the expression "a molecular sieve based on silicon and germanium" or similar expressions means that the framework of the molecular sieve contains silicon and germanium. In special cases, such expressions may mean that the framework of the molecular sieve is composed exclusively of silicon and germanium.

[0089] In the context of this specification, the expression "not more than 10% of Ge atoms in the molecular sieve are replaced by atoms of at least one element other than silicon and germanium" or similar expressions means that Ge atoms in the framework of the molecular sieve are replaced by atoms of at least one element other than silicon and germanium, and this replacing element occupies the position of the replaced Ge atom. In the context of this specification, the so-called specific surface area refers to the total area per unit mass of a sample, including the internal surface area and the external surface area. Non-porous samples, such as Portland cement, some clay mineral powders, etc., have only an external surface area; preforated porous samples, such as asbestos fibers, diatomaceous earth, and molecular sieves, have an external surface area and an internal surface area. In a porous sample having pores, the surface area of ​​pores with a pore diameter of less than 2 nm is the internal surface area, and the surface area obtained by subtracting the internal surface area is called the external surface area. The external surface area per unit mass of the sample is the external specific surface area.

[0090] In the context of this specification, the so-called pore volume refers to the volume of pores per unit mass of porous material.The so-called total pore volume refers to the volume of all pores (generally only pores with a pore diameter of less than 50 nm) per unit mass of molecular sieve.The so-called micropore volume refers to the volume of all micropores (generally pores with a pore diameter of less than 2 nm) per unit mass of molecular sieve.

[0091] In the context of this specification, as is well known to those skilled in the art, in the XRD data of molecular sieves, w, m, s and vs represent the intensity of the diffraction peaks, where w is weak, m is medium, s is strong and vs is very strong. Generally speaking, w is less than 20%, m is between 20% and 40% (excluding 40%), s is between 40% and 70% and vs is greater than 70%, where the percentages are with respect to the highest peak in the XRD pattern, i.e. the intensity of the highest peak in the XRD pattern is defined as 100%.

[0092] In the context of this specification, the structure of a molecular sieve is determined by its X-ray diffraction (XRD) pattern, which is measured by an X-ray powder diffractometer using a Cu-Kα source, a Kα1 wavelength λ=1.5405980 angstroms (Å), and a nickel filter.

[0093] In particular, it should be noted that two or more aspects (or embodiments) disclosed in the context of this specification can be arbitrarily combined with each other, and the technical solutions (such as methods or systems) formed thereby belong to part of the original disclosure of this specification and are also included within the protection scope of the present invention.

[0094] Unless expressly indicated, all percentages, parts, ratios, etc. referred to herein are by weight, unless a weight basis is in accordance with the conventional wisdom of one of ordinary skill in the art.

[0095] According to one aspect, the present invention relates to a silicon and germanium based molecular sieve having an X-ray diffraction pattern substantially as shown in the table below.

[0096] [Table 22]

[0097] According to one embodiment of the invention, the X-ray diffraction pattern also includes an X-ray diffraction pattern substantially as shown in the table below.

[0098] [Table 23]

[0099] According to one aspect of the invention, the X-ray diffraction pattern optionally further comprises X-ray diffraction peaks substantially as shown in the table below.

[0100] [Table 24]

[0101] According to one aspect of the present invention, the molecular sieve of the present invention has a framework chemical composition I, which is represented by the general formula "SiO2·1 / nGeO2". It is known that molecular sieves sometimes (especially immediately after synthesis) contain a certain amount of water. However, in the present invention, it may not be necessary to limit the amount of water, since the presence or absence of water does not substantially affect the XRD pattern of the molecular sieve. In this respect, the framework chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Furthermore, it is clear that the framework chemical composition I represents the framework chemical composition of the molecular sieve of the present invention.

[0102] According to one embodiment of the present invention, in said framework chemical composition I, the silicon / germanium molar ratio is 0.1≦n≦30, preferably 0.25≦n≦20, more preferably 0.5≦n≦15, and even more preferably 1≦n≦5.

[0103] According to one aspect of the present invention, immediately after synthesis, the molecular sieve may generally further contain organic matter (particularly organic templating agent), water, etc., for example, filled in its pores. Thus, the molecular sieve of the present invention may also have a framework chemical composition II represented by the formula "kF·mQ·SiO2·1 / nGeO2·pH2O". Here, the molecular sieve having framework chemical composition II may be calcined to remove any organic templating agent and water present in the pores to obtain a molecular sieve having framework chemical composition I. Furthermore, the calcination may be carried out by any method conventionally known in the art. For example, the calcination temperature is generally 300°C to 750°C, preferably 400°C to 600°C, and the calcination time is generally 1 hour to 10 hours, preferably 3 hours to 6 hours. Furthermore, the calcination may be carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere, and the calcination may also be carried out in situ. In this respect, framework chemistry I may also be referred to as the calcined framework chemistry, and framework chemistry II may also be referred to as the framework chemistry in its as-synthesized form.

[0104] According to one embodiment of the present invention, in said framework chemical composition II, the silicon / germanium molar ratio is 0.1≦n≦30, preferably 0.25≦n≦20, more preferably 0.5≦n≦15, and even more preferably 1≦n≦5.

[0105] According to one embodiment of the present invention, in the framework chemical composition II, F is fluorine, 0.05≦k≦1.0, preferably 0.05≦k≦0.5, more preferably 0.1≦k≦0.5, and further preferably 0.1≦k≦0.4.

[0106] According to one embodiment of the present invention, in said framework chemical composition II, Q is an organic templating agent, 0.01≦m≦1.0, preferably 0.02≦m≦0.5, more preferably 0.05≦m≦0.5, and even more preferably 0.05≦m≦0.3.

[0107] According to one aspect of the present invention, in the framework chemical composition II, the organic templating agent is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions, or is represented by the following structural formula, preferably 1,1,3,5-tetramethylpiperidinium hydroxide. These organic templating agents can be used alone or in combination with multiple organic templating agents in the required ratio.

[0108] [ka]

[0109] In the above formula, R1-R4 are each independently H or C 1-4 Alkyl, preferably C 1-2 is alkyl, more preferably -CH3; - is a halide ion (e.g., Cl - , Br - and I - ) and hydroxide ion (OH - ), preferably hydroxide ion (OH - ).

[0110] According to one embodiment of the present invention, in the framework chemical composition II, 0.005≦p≦0.5, preferably 0.01≦p≦0.4, more preferably 0.01≦p≦0.3, and further preferably 0.02≦p≦0.2.

[0111] According to one aspect of the present invention, in the molecular sieve of the present invention, the germanium of the framework can be partially replaced by a trivalent or tetravalent element other than silicon and germanium, and the replacement rate is 10% or less. Here, the parameter "replacement rate" is dimensionless. The element other than silicon and germanium is at least one selected from the group consisting of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium, and preferably at least one selected from the group consisting of aluminum and titanium. When germanium is replaced by a trivalent element such as trivalent boron or trivalent aluminum, the replacement rate = 2X2O3 / (2X2O3+GeO2) x 100%, where X is a trivalent element; when germanium is replaced by a tetravalent element such as tetravalent tin, tetravalent zirconium, or tetravalent titanium, the replacement rate = YO2 / (YO2+GeO2) x 100%, where Y is a tetravalent element. When calculating the substitution rate, the number of moles of the corresponding oxide is used.

[0112] According to one aspect of the present invention, the specific surface area (BET method) of the molecular sieve of the present invention is 200 m 2 / g~800m 2 / g, preferably 250m 2 / g~700m 2 / g.

[0113] According to one aspect of the present invention, the micropore volume (t-plot method) of the molecular sieve of the present invention is less than 0.1 cm 3 / g~0.35cm 3 / g, preferably 0.12 cm 3 / g~0.3cm 3 / g.

[0114] According to one aspect of the present invention, the molecular sieve of the present invention can be synthesized by the following method. In this respect, the present invention also relates to a method for producing a molecular sieve based on silicon and germanium. The method includes a step of crystallizing a mixture containing a silicon source, a germanium source, a fluorine source, an organic templating agent Q and water, or a mixture formed from a silicon source, a germanium source, a fluorine source, an organic templating agent Q and water (hereinafter collectively referred to as "mixture") to obtain a molecular sieve.

[0115] According to one aspect of the present invention, in the method for preparing molecular sieves, the organic templating agent is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions, or is represented by the following structural formula, preferably 1,1,3,5-tetramethylpiperidinium hydroxide: These organic templating agents can be used alone or in combination with multiple organic templating agents in the required ratio.

[0116] [ka]

[0117] R1-R4 are each independently H or C 1-4 alkyl, preferably C 1-2 is alkyl, more preferably -CH3; - is a halide ion (e.g., Cl - , Br - and I - ) and hydroxide ion (OH - ), preferably hydroxide ion (OH - ).

[0118] According to one aspect of the present invention, in the method for producing a molecular sieve, the crystallization step can be carried out by any method conventionally known in the art, for example, a method of mixing the silicon source, the germanium source, the fluorine source, the organic templating agent and water in a predetermined ratio, and subjecting the resulting mixture to hydrothermal crystallization in a crystallized state. Stirring can be optionally performed as necessary.

[0119] According to one aspect of the present invention, in the method for producing molecular sieve, the silicon source can be any silicon source that is conventionally used in the art for this purpose.For example, water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, and tetraethyl orthosilicate can be included.These silicon sources can be used alone or in combination with multiple silicon sources in desired ratio.

[0120] According to one aspect of the present invention, in the method for producing molecular sieves, the germanium source can be any germanium source conventionally used in the art for this purpose, including but not limited to germanium oxide, germanium nitrate, and germanium tetraalkoxide, where the alkoxide is a C1-C6 alkoxide.

[0121] According to one aspect of the present invention, in the process for producing a molecular sieve, the fluorine source can be any fluorine source conventionally used in the art for this purpose, such as fluoride or an aqueous solution of fluoride, such as hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride, and in particular hydrofluoric acid.

[0122] According to one aspect of the present invention, in the method for producing a molecular sieve, the molar ratio of the organic templating agent Q, the silicon source (as SiO2), the germanium source (as GeO2), the fluorine source (as F) and water is Q:SiO2:GeO2:F:H2O=0.15-4:1:0.033-10:0.2-4:0.5-50, preferably Q:SiO2:Ge O2:F:H2O=0.25-3.5:1:0.05-4:0.35-3.5:1-35, more preferably Q:SiO2:GeO2:F:H2O=0.3-2.5:1:0.067-2:0.4-2.5:1.5-25, and even more preferably Q:SiO2:GeO2:F:H2O=0.35-1.5:1:0.2-1:0.45-2:2-15.

[0123] According to one embodiment of the present invention, in the method for producing a molecular sieve, the crystallization conditions include crystallization at 100°C to 200°C for 30 hours to 400 hours; preferably crystallization at 110°C to 190°C for 48 hours to 360 hours; more preferably crystallization at 120°C to 180°C for 72 hours to 320 hours, for example, crystallization at 120°C to 180°C for 72 hours to 32 hours.

[0124] According to one aspect of the present invention, in the method for producing molecular sieves, when a trivalent or tetravalent element other than silicon and germanium replaces a germanium atom, it is necessary to add an oxide source of a trivalent or tetravalent element other than silicon and germanium, preferably a trivalent or tetravalent element other than silicon and germanium, to the mixture.The oxide source preferably includes at least one oxide source selected from the group consisting of a boron oxide source, an alumina source, a gallium oxide source, a titania source, a zirconia source, a hafnia source, a tin oxide source, a zinc oxide source, a iron oxide source, a chromium oxide source and an indium oxide source; the alumina source may specifically include at least one selected from the group consisting of aluminum hydroxide, sodium aluminate, an aluminum salt, kaolin and montmorillonite.The boron oxide source may specifically include at least one selected from the group consisting of boron oxide, borax, sodium metaborate and boric acid. Specific examples of the tin oxide source include at least one selected from the group consisting of tin tetrachloride, stannous chloride, alkyl tin, tin alkoxide, and organic stannate ester. Specific examples of the zirconia source include at least one selected from the group consisting of zirconium salts (zirconium nitrate, zirconium sulfate, etc.), alkyl zirconium, zirconium alkoxide, and organic zirconate ester. Specific examples of the titania source include at least one selected from the group consisting of tetraalkyl titanates (tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra-n-butyl titanate, etc.), TiCl4, hexafluorotitanic acid, Ti(SO4)2, and hydrolysates thereof.The gallium oxide source may specifically include at least one selected from the group consisting of gallium nitrate, gallium oxide, gallium halides (such as gallium chloride and gallium bromide), gallium sulfate, gallium isopropoxide, gallium acetate, and gallium ethoxide; the hafnia source may specifically include at least one selected from the group consisting of hafnia, hafnium halides (such as hafnium chloride and hafnium bromide), hafnium sulfate, hafnium t-butoxide, hafnium oxychloride, and hafnium ethoxide. Specific examples of the zinc oxide source include at least one selected from the group consisting of zinc oxide, zinc halide (e.g., zinc chloride), zinc acetate, basic zinc carbonate, zinc sulfate, zinc nitrate, zinc lactate, and zinc gluconate; Specific examples of the iron oxide source include at least one selected from the group consisting of iron sulfate, iron nitrate, iron halide (e.g., iron trichloride), ferrocene, and iron citrate; Specific examples of the chromium oxide source include at least one selected from the group consisting of dichromium trioxide, chromium chloride, chromium nitrate, chromium acetate, and chromic potassium sulfate; and Specific examples of the indium oxide source include at least one selected from the group consisting of indium oxide, indium sulfate, indium halide (e.g., indium trichloride), and indium acetate.

[0125] According to one aspect of the present invention, when used in a method for producing a molecular sieve, the molar ratio of the oxide source (as the corresponding oxide) to the germanium source (as GeO2) is generally (0.01-0.1):1, preferably (0.015-0.08):1.

[0126] According to one aspect of the present invention, in the method for producing molecular sieves, after the crystallization is completed, the product molecular sieve can be separated from the resulting reaction mixture by any conventional separation method, and the molecular sieve of the present invention thus obtained is also known as the molecular sieve of the present invention in the form of a synthesis, for example, by filtering, washing, and drying the resulting reaction mixture.

[0127] According to one aspect of the present invention, in the method for producing a molecular sieve, filtration, washing and drying can be carried out by any method conventionally known in the art. Specifically, as one example, the filtration may be performed by simply subjecting the obtained reaction mixture to suction filtration. The washing may be performed by using deionized water. The drying temperature may be, for example, 40°C to 250°C, preferably 60°C to 150°C; the drying time may be, for example, 8 hours to 30 hours, preferably 10 hours to 20 hours. Drying may be performed under normal pressure or reduced pressure.

[0128] According to one aspect of the present invention, in the method for producing molecular sieves, the molecular sieve obtained by crystallization can be calcined, since it is necessary to remove organic templating agents, water that may be present, etc., and the calcined molecular sieve obtained thereby is also known as the calcined form of the molecular sieve of the present invention. The calcination can be carried out by any method conventionally known in the art. For example, the calcination temperature is generally 300°C to 800°C, preferably 400°C to 650°C, and the calcination time is generally 1 hour to 10 hours, preferably 3 hours to 6 hours. Furthermore, the calcination can be carried out in an oxygen-containing atmosphere such as air or an oxygen atmosphere, and the calcination can also be carried out in situ. Preferably, the calcination is carried out in situ.

[0129] According to one aspect of the present invention, the molecular sieve of the present invention can be in any physical form, for example, in the form of a powder, granules, or moldings (e.g., strips, trefoils, etc.). These physical forms can be obtained by any method conventionally known in the art and are not particularly limited.

[0130] According to one aspect of the present invention, the molecular sieve of the present invention can be used in combination with other materials, thereby obtaining a molecular sieve composition. These other materials can include, for example, active materials and inactive materials. The active materials can include, for example, synthetic zeolites, natural zeolites, etc.; the inactive materials (generally referred to as binders) can include, for example, clay, kaolin, silica gel, alumina, etc. These other materials can be used alone or in combination with multiple other materials in any ratio. The amount of the other materials used can be directly referred to the amount used in the past in the art, and there is no particular limitation in this regard.

[0131] According to one aspect of the invention, the molecular sieve or molecular sieve composition of the invention can be used as an adsorbent, for example, to separate at least one component from a mixture of multiple components in a gas or liquid phase. Thus, at least one component can be partially or substantially completely separated from a mixture of various components by contacting the mixture with the molecular sieve or molecular sieve composition of the invention and selectively adsorbing this component.

[0132] According to one aspect of the invention, the molecular sieve or molecular sieve composition of the invention can also be used as a catalyst (or as a catalytically active component) either directly or after any treatment or transformation (e.g. for ion exchange, etc.) necessary for molecular sieves as conventional in the art. For this purpose, according to one aspect of the invention, for example, reactants (e.g. hydrocarbons) are subjected to a given reaction in the presence of said catalyst, thereby obtaining the desired product.

[0133] The present invention will be described in more detail in the following specific examples, but the scope of protection of the present invention is not limited to the following examples.

[0134] Example 1 7 g of germanium oxide was dissolved in 76.8 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 27.8 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water and ethanol. 5 g of hydrofluoric acid (40 wt%) was added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.5(1,1,3,5-TMPOH):0.667SiO2:0.333GeO2:0.5HF:7H2O The mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 170° C. for 288 hours. After the reaction, the solid was filtered, washed, dried, and calcined in air to obtain molecular sieves. The specific surface area of ​​the resulting molecular sieve product was 498 m 2 / g, micropore volume is 0.18 cm 3 The XRD pattern of the sample before calcination is shown in Figure 1, the XRD pattern after calcination is shown in Figure 2, a scanning electron micrograph is shown in Figure 3, and the N2 adsorption-desorption isotherm at 77 K is shown in Figure 4.

[0135] [Table 25]

[0136] The XRD pattern of the product after in situ calcination was consistent with the XRD pattern in FIG. 1, and the characteristic data of the XRD pattern and the calculated interplanar spacing data are shown in the above table.

[0137] Example 2 4.2 g of germanium oxide was dissolved in 115 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 33.3 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate some of the ethanol and water. 10 g of ammonium fluoride solution (37 wt%) was added, the mixture was stirred uniformly, and some of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.75(1,1,3,5-TMPOH):0.8SiO2:0.2GeO2:0.5NH4F:2.5H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 160° C. for 240 hours. After the reaction, the solid was filtered, washed, dried, and calcined in air to obtain the molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2.

[0138] [Table 26]

[0139] The characteristic data of the XRD patterns and the calculated interplanar spacing data of the products after in situ calcination are shown in the table above.

[0140] Example 3 10.5 g of germanium oxide was dissolved in 61.4 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 20.8 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water and ethanol. 5 g of hydrofluoric acid (40 wt%) and 10 g of ammonium fluoride solution (37 wt%) were added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.4(1,1,3,5-TMPOH):0.5SiO2:0.5GeO2:0.5HF:0.5NH4F:4.8H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 175° C. for 216 hours. After the reaction, the solid was filtered, washed, dried, and calcined in air to obtain the molecular sieve. The XRD pattern of the obtained molecular sieve was similar to the XRD pattern in FIG. 2.

[0141] [Table 27]

[0142] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0143] Example 4 14 g of germanium oxide was dissolved in 153.6 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 13.9 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water and ethanol. 12 g of hydrofluoric acid (40 wt%) was added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 1(1,1,3,5-TMPOH):0.333SiO2:0.667GeO2:1.2HF:13.5H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 165° C. for 180 hours. After the reaction, the solid was filtered, washed, dried, and calcined in air to obtain the molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2.

[0144] [Table 28]

[0145] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0146] Example 5 3.5 g of germanium oxide was dissolved in 192 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 34.5 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water and ethanol. 60 g of ammonium fluoride solution (37 wt%) was added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 1.25(1,1,2,5-TMPOH):0.833SiO2:0.167GeO2:3NH4F:22H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 150° C. for 192 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain the molecular sieve. The XRD pattern of the obtained molecular sieve was similar to the XRD pattern in FIG. 2.

[0147] [Table 29]

[0148] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0149] Example 6 0.4 g of aluminum isopropoxide and 7 g of germanium oxide were dissolved in 76.8 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 27.8 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water, propanol and ethanol. 10 g of hydrofluoric acid (40 wt%) was added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.5(1,1,3,5-TMPOH):0.667SiO2:0.333GeO2:0.005Al2O3:1HF:5H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 165° C. for 250 hours. After the reaction, the solid was filtered, washed, dried, and calcined to obtain a solid, i.e., aluminum-containing molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2, and (Si+Ge) / Al=130 in the product.

[0150] [Table 30]

[0151] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0152] Example 7 2 g of aluminum isopropoxide and 10.5 g of germanium oxide were dissolved in 76.8 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 20.8 g of tetraethyl orthosilicate (TEOS) was slowly added. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water, propanol and ethanol. 10 g of hydrofluoric acid (40 wt%) and 10 g of ammonium fluoride solution (37 wt%) were added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.5(1,1,3,5-TMPOH):0.5SiO2:0.5GeO2:0.025Al2O3:1HF:0.5NH4F:8H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 155° C. for 300 hours. After the reaction, the solid was filtered, washed, dried and calcined to obtain a solid, i.e., aluminum-containing molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2, and (Si+Ge) / Al=28 in the product.

[0153] [Table 31]

[0154] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0155] Example 8 12.4g of germanium oxide was dissolved in 92g of 1,1,3,5-TMPOH aqueous solution (20wt%), 1g of Ludox-AS-40 silica sol and 4.6g of USY zeolite (SiO2 / Al2O3=37). After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water. 28g of ammonium fluoride solution (37wt%) was added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.6(1,1,3,5-TMPOH):0.4SiO2:0.6GeO2:0.01Al2O3:1.4NH4F:16.5H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 185° C. for 168 hours. After reaction, the solid was filtered, washed, dried and calcined to obtain a solid, i.e., aluminum-containing molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2, and the (Si+Ge) / Al=57 in the product.

[0156] [Table 32]

[0157] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0158] Example 9 7 g of germanium oxide was dissolved in 76.8 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 27.8 g of tetraethyl orthosilicate (TEOS) was slowly added. After completion of hydrolysis, 2 g of ferric nitrate nonahydrate was added.

[0159] The vessel was opened and stirred overnight to evaporate part of the water and ethanol. 5 g of hydrofluoric acid (40 wt%) and 30 g of ammonium fluoride solution (37 wt%) were added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.5(1,1,3,5-TMPOH):0.667SiO2:0.333GeO2:0.0125Fe2O3:0.5HF:1.5NH4F:6.6H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 130° C. for 192 hours. After the reaction, the solid was filtered, washed, dried and calcined to obtain a solid, i.e., iron-containing molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2, and the (Si+Ge) / Fe=30 in the product.

[0160] [Table 33]

[0161] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0162] Example 10 7 g of germanium oxide was dissolved in 123 g of 1,1,3,5-TMPOH aqueous solution (20 wt%), and 27.8 g of tetraethyl orthosilicate (TEOS) was slowly added. The mixture was stirred uniformly, and 1.7 g of tetrabutyl titanate was slowly added dropwise. The mixture was stirred at room temperature. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water, butanol, and ethanol. 20 g of hydrofluoric acid (40 wt%) was added, and the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 0.8(1,1,3,5-TMPOH):0.667SiO2:0.333GeO2:0.025TiO2:2HF:12H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 175° C. for 144 hours. After the reaction, the solid was filtered, washed, dried and calcined to obtain a solid, i.e., titanium-containing molecular sieve. The XRD pattern of the obtained molecular sieve was similar to that in FIG. 2, and the (Si+Ge) / Ti=41 in the product.

[0163] [Table 34]

[0164] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above.

[0165] Example 11 4g of germanium oxide, 5g of white carbon black and 0.145g of boric acid were dissolved in 90.4g of 1,1,3,5-TMPOH aqueous solution (20wt%), and 0.59g of tetrabutyl titanate was slowly added dropwise. After completion of hydrolysis, the vessel was opened and stirred overnight to evaporate part of the water and butanol. 23.5g of ammonium fluoride solution (37wt%) was added, the mixture was stirred uniformly, and part of the water was continued to evaporate until the reaction mixture reached the following molar composition: 1(1,1,3,5-TMPOH):0.667SiO2:0.333GeO2:0.01B2O3:0.015TiO2:2NH4F:9.5H2O The above mixture was loaded into a Teflon-lined crystallization autoclave and crystallized in an oven at 180° C. for 168 hours. After the reaction, the solid was filtered, washed, dried and calcined to obtain the solid, i.e., boron-containing and titanium-containing molecular sieves. The XRD pattern of the obtained molecular sieves was similar to that in FIG. 2, and (Si+Ge) / B=55, (Si+Ge) / Ti=60 in the product.

[0166] [Table 35]

[0167] The characteristic data of the XRD patterns of the products after in situ calcination and the calculated interplanar spacing data are given in the table above. [Brief description of the drawings]

[0168] [Figure 1] 1 is an X-ray diffraction (XRD) pattern of a sample before firing obtained in Example 1. [Diagram 2] 1 is an X-ray diffraction (XRD) pattern of a fired sample obtained in Example 1. [Diagram 3] 1 is a scanning electron microscope (SEM) photograph of a sample obtained in Example 1. [Figure 4] 1 is a N2 adsorption-desorption isotherm at 77 K for the sample obtained in Example 1.

Claims

1. A molecular sieve having an X-ray diffraction pattern as shown in the table below, 【Table 1】 The molecular sieve, wherein the molecular sieve is based on silicon and germanium.

2. The molecular sieve described in claim 1, wherein the X-ray diffraction pattern further includes the X-ray diffraction peaks shown in the table below. 【Table 2】

3. 3. The molecular sieve of claim 1 or 2, wherein the molecular sieve has an X-ray diffraction pattern as shown in the table below. 【Table 3】

4. The molecular sieve of any one of claims 1 to 3, wherein the molecular sieve has an X-ray diffraction pattern as shown in the table below. 【Table 4】

5. The molecular sieve of any one of claims 1 to 4, wherein the molecular sieve has an X-ray diffraction pattern as shown in the table below. 【Table 5】

6. The molecular sieve of any one of claims 1 to 5, wherein the molecular sieve has an X-ray diffraction pattern as shown in the table below. 【Table 6】

7. The molecular sieve of any one of claims 1 to 6, wherein the molecular sieve has an X-ray diffraction pattern as shown in the table below. 【Table 7】

8. The calcined form of the molecular sieve is represented by the formula "SiO ２ 1 / nGeO ２ " and has a skeleton chemical composition represented by the formula:

8. The molecular sieve according to claim 1, wherein the molar ratio of silicon to germanium is 0.1≦n≦30.

9. The molecular sieve in as-synthesized form has the formula "kF.mQ.SiO ２ 1 / nGeO ２ pH ２ O" The silicon / germanium molar ratio is 0.1≦n≦30; 0.05≦k≦1.0; Q is an organic templating agent, 0.01≦m≦1.0; The organic templating agent is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions, or is represented by the following structural formula: 【Chemistry 1】 In the above formula, R １ -R ４ are each independently H or C １－４ alkyl, and X − is Cl − , Br − , I − , or a hydroxide ion (OH − ); The molecular sieve according to any one of claims 1 to 8, wherein 0.005≦p≦0.

5.

10. 10. The molecular sieve of claim 1, wherein up to 10% of the Ge atoms in the molecular sieve are replaced by atoms of at least one element other than silicon and germanium.

11. 11. The molecular sieve of claim 10, wherein the element other than silicon and germanium is at least one selected from the group consisting of boron, aluminum, gallium, titanium, zirconium, hafnium, tin, zinc, iron, chromium and indium.

12. The method includes a step of crystallizing a mixture comprising a silicon source, a germanium source, a fluorine source, an organic templating agent Q and water, or a mixture formed from a silicon source, a germanium source, a fluorine source, an organic templating agent Q and water, to obtain a molecular sieve; and optionally, calcining the resulting molecular sieve; The organic templating agent Q is selected from quaternary ammonium forms including 1,1,3,5-tetraalkylpiperidinium ions, or is represented by the following structural formula: 【Chemistry 2】 R １ -R ４ are each independently H or C １－４ is alkyl, and X － is Cl － , B － , I － , or hydroxide ion (OH － ) A method for producing a molecular sieve.

13. The silicon source is at least one selected from the group consisting of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomaceous earth, zeolite, and tetraethyl orthosilicate; The germanium source is at least one selected from the group consisting of germanium oxide, germanium nitrate, and germanium tetraalkoxide, and the alkyloxy in the germanium tetraalkoxide is C １ -C ６ alkyloxy; The organic templating agent Q, the silicon source (SiO ２ as the germanium source (GeO ２ as fluorine source), the molar ratio of the fluorine source (as F) and water is ２ : GeO ２ :F:H ２ The method for producing a molecular sieve according to claim 12, characterized in that O=0.15-4:1:0.033-10:0.2-4:0.5-50.

14. 13. The method for producing a molecular sieve according to claim 12, wherein the fluorine source comprises at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride.

15. The method for producing a molecular sieve described in claim 12, characterized in that the conditions in the crystallization process include crystallization at 100°C to 200°C for 30 hours to 400 hours.

16. The mixture further comprises a source comprising an element other than silicon and germanium; the source is at least one oxide source selected from the group consisting of a boron oxide source, an alumina source, a gallium oxide source, a titania source, a zirconia source, a hafnia source, a tin oxide source, a zinc oxide source, an iron oxide source, a chromium oxide source, and an indium oxide source; The germanium source (GeO ２ The method for producing a molecular sieve according to claim 12, characterized in that the molar ratio of (as) to (as) is (0.01-0.1):

1.

17. A molecular sieve composition comprising the molecular sieve of any one of claims 1 to 11 and a binder.

18. Use of the molecular sieve according to any one of claims 1 to 11, the molecular sieve produced by the method for producing a molecular sieve according to any one of claims 12 to 16, or the molecular sieve composition according to claim 17 as an adsorbent or catalyst.

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